1-(heterocyclic carbonyl)-2-substituted pyrrolidines

ABSTRACT

The present invention relates to fungicidal 1-(heterocyclic carbonyl)-2-substituted pyrrolidines and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

The present invention relates to fungicidal 1-(heterocycliccarbonyl)-2-substituted pyrrolidines and their thiocarbonyl derivatives,their process of preparation and intermediate compounds for theirpreparation, their use as fungicides, particularly in the form offungicidal compositions and methods for the control of phytopathogenicfungi of plants using these compounds or their compositions.

In international patent application WO-2009/153191 certain fungicidalproline amides are generically embraced in a broad disclosure ofnumerous compounds of the following formula:

wherein A can represent a substituted pyrazole or a substitutedpyridine, R₁ and R₂ can represent various substituent among which ahydrogen atom or a C₁-C₆-alkyl group, G can represent a bond, an oxygenatom, a sulfur atom, a CH₂ or a (CH₂)₂ moiety, and B can represent a(un)substituted phenyl ring. However, there is no disclosure orsuggestion in this document of any such derivative bearing a(hetero)aryl ring directly linked to the pyrrolidine moiety.Furthermore, there is no explicite disclosure or suggestion to select inthis document of any such derivative wherein A represents a 3-(difluoroor dichloro)methyl-5-(chloro or fluoro)-1-methyl-4-pyrazolyl group.

In international patent application DE3641343 certain fungicidalheterocyclylcarbonylimidazoles are generically embraced in a broaddisclosure of numerous compounds of the following formula:

wherein Y can represent a hydrogen atom or a phenyl ring, n can be equalto 2 to 6, m can be equal to 1 to 2, and R can represent varioussubstituent among which a (het)aryloxy group, a (het)aryloxymethylgroup, a (het)arylsulfanylmethyl group or a (het)aryloxyethyl group.However, there is no disclosure or suggestion to select in this documentof any such derivative wherein the imidazole moiety can be replaced by a3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-1-methyl-4-pyrazolylgroup.

In international patent application U.S. Pat. No. 4,589,905 certainherbicidal and algicidal 5-cyano-4-carboxamide pyrazoles are genericallyembraced in a broad disclosure of numerous compounds of the followingformula:

wherein X can be O or S, R¹ can represent a C₁-C₆ alkyl group, a C₅-C₆cycloalkyl group or a (het)aromatic group, and R² and R³ taken togetherwith the nitrogen atom can represent a piperidine, a morpholine or apyrrolidine ring. However, there is no disclosure or suggestion toselect in this document of any such derivative wherein the pyrrolidinering can be sustituted in the 2-position by any substituent. Morewever,there is no disclosure or suggestion in this document of any use of suchderivatives as antifungal or antimicrobial compounds.

It is always of high-interest in the field of agrochemicals to usepesticidal compounds more active than the compounds already known by theman ordinary skilled in the art whereby reduced amounts of compound canbe used whilst retaining equivalent efficacy.

Furthermore, the provision of new pesticidal compounds with a higherefficacy strongly reduces the risk of appearance of resistant strains inthe fungi to be treated.

We have now found a new family of compounds which show enhancedfungicidal activity over the general known family of such compounds.

Accordingly, the present invention provides a1-(heterocyclic[thio]carbonyl) pyrrolidine derivative of formula (I)

wherein

-   -   T represents O or S;    -   X¹ and X² which can be the same or different, represent a        chlorine or a fluorine atom;    -   n represents 0, 1 or 2;    -   Q¹ represents a bond; 0; S; SO; or SO₂;    -   B represents a phenyl ring that can be substituted by up to 5        groups X which can be the same or different; a naphthyl ring        that can be substituted by up to 7 groups X which can be the        same or different; or a saturated, partially saturated or        unsaturated, monocyclic or fused bicyclic 4-, 5-, 6-, 7-, 8-,        9-, 10-membered ring comprising from 1 up to 4 heteroaroms        selected in the list consisting of N, O, S, that can be        substituted by up to 6 groups X which can be the same or        different;    -   X represents a halogen atom; nitro; cyano; isonitrile; hydroxy;        amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy;        formylamino; substituted or non-substituted        (hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted        (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted        (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or        non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted        or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;        carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or        non-substituted C₁-C₈ alkyl; C₁-C₈-halogenoalkyl having 1 to 5        halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;        C₂-C₈-halogenoalkenyl having 1 to 5 halogen atoms; substituted        or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1        to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;        C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms; substituted or        non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl        having 1 to 5 halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy        having 1 to 5 halogen atoms; substituted or non-substituted        C₃-C₈-alkynyloxy; C₂-C₈-halogenoalkynyloxy having 1 to 5 halogen        atoms; substituted or non-substituted C₃-C₇-cycloalkyl;        C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl;        substituted or non-substituted tri(C₁-C₈)alkylsilyl; substituted        or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted        or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbonyloxy;        C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbonylamino;        C₁-C₈-halogenoalkyl-carbonylamino having 1 to 5 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms;        substituted or non-substituted C₁-C₈-alkyloxycarbonyloxy;        C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted        or non-substituted di-C₁-C₈-alkylcarbamoyl; substituted or        non-substituted C₁-C₈-alkylaminocarbonyloxy; substituted or        non-substituted di-C₁-C₈-alkylaminocarbonyloxy; substituted or        non-substituted N—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or        non-substituted C₁-C₈-alkoxycarbamoyl; substituted or        non-substituted N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that        can be substituted by up to 6 groups Q which can be the same or        different; C₁-C₈-arylalkyl that can be substituted by up to 6        groups Q which can be the same or different; C₂-C₈-arylalkenyl        that can be substituted by up to 6 groups Q which can be the        same or different; C₂-C₈-arylalkynyl that can be substituted by        up to 6 groups Q which can be the same or different; aryloxy        that can be substituted by up to 6 groups Q which can be the        same or different; arylsulfanyl that can be substituted by up to        6 groups Q which can be the same or different; arylamino that        can be substituted by up to 6 groups Q which can be the same or        different; C₁-C₈-arylalkyloxy that can be substituted by up to 6        groups Q which can be the same or different;        C₁-C₈-arylalkylsulfanyl that can be substituted by up to 6        groups Q which can be the same or different; or        C₁-C₈-arylalkylamino that can be substituted by up to 6 groups Q        which can be the same or different;    -   two substituent X together with the consecutive carbon atoms to        which they are linked can form a 5- or 6-membered, saturated        carbocycle or saturated heterocycle, which can be substituted by        up to four groups Q which can be the same or different;    -   Z¹ and Z² independently represent a hydrogen atom; a halogen        atom; cyano; substituted or non-substituted C₁-C₈-alkyl;        C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted or        non-substituted C₁-C₈-alkoxy; substituted or non-substituted        C₁-C₈-alkylsulfanyl; or substituted or non-substituted        C₁-C₈-alkoxycarbonyl; or    -   two substituents Z¹ and Z², together with the carbon atom to        which they are linked can form a 3-, 4-, 5- or 6-membered        saturated carbocycle that can be substituted by up to four        C₁-C₈-alkyl groups;    -   Z³ represent a hydrogen atom; or substituted or non-substituted        C₁-C₈-alkyl;    -   Q independently represents a halogen atom; cyano; nitro;        substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl        having 1 to 9 halogen atoms that can be the same or different;        substituted or non-substituted C₁-C₈-alkoxy;        C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms that can be the        same or different; substituted or non-substituted        C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9        halogen atoms that can be the same or different; substituted or        non-substituted tri(C₁-C₈)alkylsilyl; substituted or        non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or        non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or        non-substituted (benzyloxyimino)-C₁-C₈-alkyl;    -   as well as its salts, N-oxides, metal complexes, metalloid        complexes and optically active isomers.

For the compounds according to the invention, the following genericterms are generally used with the following meanings:

-   -   halogen means fluorine, bromine, chlorine or iodine.    -   carboxy means —C(═O)OH;    -   carbonyl means —C(═O)—;    -   carbamoyl means —C(═O)NH₂;    -   N-hydroxycarbamoyl means —C(═O)NHOH;    -   SO represents a sulfoxide group;    -   SO₂ represents a sulfone group;    -   an alkyl group, an alkenyl group and an alkynyl group as well as        moieties containing these terms, can be linear or branched;    -   the aryl moiety contained in an aryl group, an arylalkyl group,        an arylalkenyl group and an arylalkynyl group as well as        moieties containing these terms, can be a phenyl group that can        be substituted by up to 5 groups Q which can be the same or        different, a naphthyl group that can be substituted by up to 7        groups Q which can be the same or different or a pyridyl group        that can be substituted by up to 4 groups Q which can be the        same or different;    -   heteroatom means sulfur, nitrogen or oxygen.    -   in the case of an amino group or the amino moiety of any other        amino-comprising group, substituted by two substituent that can        be the same or different, the two substituent together with the        nitrogen atom to which they are linked can form a heterocyclyl        group, preferably a 5- to 7-membered heterocyclyl group, that        can be substituted or that can include other hetero atoms, for        example a morpholino group or piperidinyl group.    -   unless indicated otherwise, a group or a substituent that is        substituted according to the invention can be substituted by one        or more of the following groups or atoms: a halogen atom, a        nitro group, a hydroxy group, a cyano group, an amino group, a        sulfanyl group, a pentafluoro-λ⁶-sulfanyl group, a formyl group,        a formyloxy group, a formylamino group, a carbamoyl group, a        N-hydroxycarbamoyl group, a carbamate group, a        (hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a        tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl, C₁-C₈-cycloalkyl,        tri(C₁-C₈-alkyl)silyl-C₁-C₈-cycloalkyl, a C₁-C₈-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₈-halogenocycloalkyl having 1        to 5 halogen atoms, a C₂-C₈-alkenyl, a C₂-C₈-alkynyl, a        C₂-C₈-alkenyloxy, a C₂-C₈-alkynyloxy, a C₁-C₈-alkylamino, a        di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy        having 1 to 5 halogen atoms, a C₁-C₈-alkylsulfanyl, a        C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a        C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5        halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy        having 1 to 5 halogen atoms, a C₁-C₈-alkylcarbonyl, a        C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, a        N—C₁-C₈-alkyloxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, a        N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, a        C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having        1 to 5 halogen atoms, a C₁-C₈-alkylcarbonylamino, a        C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a        C₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, a        C₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulfinyl, a        C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylsulfonyl, a C₁-C₈-halogenoalkylsulfonyl having 1 to 5        halogen atoms, a C₁-C₈-alkylaminosulfamoyl, a        di-C₁-C₈-alkylaminosulfamoyl, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl,        a (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a        (C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a 2-oxopyrrolidin-1-yl,        (benzyloxyimino)-C₁-C₆-alkyl, C₁-C₈-alkoxyalkyl,        C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms,        benzyloxy, benzylsulfanyl, benzylamino, phenoxy, phenylsulfanyl,        or phenylamino.

Any of the compounds of the present invention can exist in one or moreoptical or chiral isomer forms depending on the number of asymmetriccentres in the compound. The invention thus relates equally to all theoptical isomers and to their racemic or scalemic mixtures (the term“scalemic” denotes a mixture of enantiomers in different proportions)and to the mixtures of all the possible stereoisomers, in allproportions. The diastereoisomers and/or the optical isomers can beseparated according to the methods which are known per se by the manordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the number of double bonds inthe compound. The invention thus relates equally to all geometricisomers and to all possible mixtures, in all proportions. The geometricisomers can be separated according to general methods, which are knownper se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the relative position (syn/antior cis/trans) of the substituents of ring B. The invention thus relatesequally to all syn/anti (or cis/trans) isomers and to all possiblesyn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (orcis/trans) isomers can be separated according to general methods, whichare known per se by the man ordinary skilled in the art.

Any of the compounds of formula (I) wherein X represents a hydroxy, asulfanyl group or an amino group may be found in its tautomeric formresulting from the shift of the proton of said hydroxy, sulfanyl oramino group. Such tautomeric forms of such compounds are also part ofthe present invention. More generally speaking, all tautomeric forms ofcompounds of formula (I) wherein X represents a hydroxy, a sulfanylgroup or an amino group, as well as the tautomeric forms of thecompounds which can optionally be used as intermediates in thepreparation processes and which will be defined in the description ofthese processes, are also part of the present invention.

Preferred compounds of formula (I) according to the invention are thosewherein X¹ represents a fluorine atom.

Other preferred compounds of formula (I) according to the invention arethose wherein X² represents a fluorine atom.

Other preferred compounds according to the invention are compounds offormula (I) wherein T represents O.

Other preferred compounds according to the invention are compounds offormula (I) wherein n represents 0 or 1.

Other preferred compounds according to the invention are compounds offormula (I) wherein Q¹ represents a bond or an oxygen atom; other morepreferred compounds according to the invention are compounds of formula(I) wherein Q¹ represents a bond.

Other preferred compounds according to the invention are compounds offormula (I) wherein B represents a substituted or non-substituted phenylring; a substituted or non-substituted naphthyl ring; a substituted ornon-substituted pyridyl ring; a substituted or non-substituted thienylring; or a substituted or non-substituted benzothienyl ring; morepreferred compounds according to the invention are compounds of formula(I) wherein B represents a substituted or non-substituted phenyl ring;other more preferred compounds according to the invention are compoundsof formula (I) wherein B represents a substituted or non-substitutednaphthyl ring.

Other preferred compounds according to the invention are compounds offormula (I) wherein X independently represents a halogen atom;substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different;substituted or non-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxycomprising up to 9 halogen atoms that can be the same or different; orwherein two consecutive substituents X together with the phenyl ringform a substituted or non substituted 1,3-benzodioxolyl or1,4-benzodioxanyl ring.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z¹ and Z² independently represents a hydrogen atom,a halogen, substituted or non-substituted C₁-C₈-alkyl or substituted ornon-substituted C₁-C₈-alkoxy.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z³ represents a hydrogen atom.

The above mentioned preferences with regard to the substituents of thecompounds according to the invention can be combined in various manners.These combinations of preferred features thus provide sub-classes ofcompounds according to the invention. Examples of such sub-classes ofpreferred compounds according to the invention can be combined:

-   -   preferred features of X¹ with preferred features of X², T, Q¹,        B, n, Z¹ to Z³ and/or X;    -   preferred features of X² with preferred features of X¹, T, Q¹,        B, n, Z¹ to Z³ and/or X;    -   preferred features of T with preferred features of X¹, X², Q¹,        B, n, Z¹ to Z³ and/or X;    -   preferred features of Q¹ with preferred features of X¹, X², T,        B, n, Z¹ to Z³ and/or X;    -   preferred features of B with preferred features of X¹, X², T,        Q¹, n, Z¹ to Z³ and/or X;    -   preferred features of n with preferred features of X¹, X², T,        Q¹, B, Z¹ to Z³ and/or X;    -   preferred features of Z¹ with preferred features of X¹, X², T,        Q¹, B, n, Z², Z³ and/or X;    -   preferred features of Z² with preferred features of X¹, X², T,        Q¹, B, n, Z¹, Z² and/or X;    -   preferred features of Z³ with preferred features of X¹, X², T,        Q¹, B, n, Z², Z³ and/or X;    -   preferred features of X with preferred features of X¹, X², T,        Q¹, B, n, and/or Z¹ to Z³;

In these combinations of preferred features of the substituents of thecompounds according to the invention, the said preferred features canalso be selected among the more preferred features of each of X¹, X², T,Q¹, B, n, Z¹ to Z³ and X so as to form most preferred subclasses ofcompounds according to the invention.

The present invention also relates to a process for the preparation ofthe compound of formula (I).

Thus, according to a further aspect of the present invention there isprovided a process P1 for the preparation of a compound of formula (I)as herein-defined and wherein T represents O and that comprises reactinga pyrrolidine of formula (II) or one of its salts:

wherein Z¹, Z², Z³, n, Q¹ and B are as herein-defined; with a carboxylicacid derivative of formula (III):

wherein X¹ and X² are as herein-defined and L¹ represents a leavinggroup selected in the list consisting of a halogen atom, a hydroxylgroup, —OR^(a), —OC(═O)R^(a), R^(a) being a substituted ornon-substituted C₁-C₆-alkyl, a substituted or non-substitutedC₁-C₆-haloalkyl, a benzyl, 4-methoxybenzyl or pentafluorophenyl group,or a group of formula O—C(═O)A; in the presence of a catalyst and in thepresence of a condensing agent in case L¹ represents a hydroxyl group,and in the presence of an acid binder in case L¹ represents a halogenatom.

Pyrrolidines of formula (II) wherein n is equal to 0 can be prepared bydeprotonation of N-Boc-pyrrolidine and transmetallation of the anion bya zinc salt followed by a palladium coupling with (het)aryl bromides andfurther Boc deprotection (Tetrahedron Letters (1989), 30(10), 1197-1200and patent application WO-2008/53319). Pyrrolidines of formula (II)wherein n is equal to 1 can be prepared by cyclisation of substitutedN-Boc pent-4-en-1-amines followed by a palladium coupling with (het)arylbromides and further Boc deprotection (Journal of Organic Chemistry(2008), 73, 8851-8860). Pyrrolidines of formula (II) wherein n is equalto 1 or 2 can also be prepared by deprotonation of N-Boc-pyrrolidine andcondensation of a (het)arylalkyl bromide and further Boc deprotection(European Journal of Organic Chemistry (2009), 1173-1180).

Carboxylic acid derivatives of formula (III) can be prepared accordingto process P2.

In case L¹ represents a hydroxy group, the process according to thepresent invention is conducted in the presence of condensing agent.Suitable condensing agent may be selected in the non limited listconsisting of acid halide former, such as phosgene, phosphoroustribromide, phosphorous trichloride, phosphorous pentachloride,phosphorous trichloride oxide or thionyl chloride; anhydride former,such as ethyl chloroformate, methyl chloroformate, isopropylchloroformate, isobutyl chloroformate or methanesulfonyl chloride;carbodiimides, such as N,N′-dicyclohexylcarbodiimide (DCC) or othercustomary condensing agents, such as phosphorous pentoxide,polyphosphoric acid, N,N′-carbonyl-diimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),triphenylphosphine/tetrachloro-methane,4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloridehydrate, bromo-tripyrrolidinophosphonium hexafluorophosphate andpropanephosphonic anhydride (T3P).

The process according to the present invention is conducted in thepresence of a catalyst. Suitable catalyst may be selected in the listconsisting of 4-dimethyl-aminopyridine, 1-hydroxy-benzotriazole ordimethylformamide.

In case L¹ represents a halogen atom, the process according to thepresent invention is conducted in the presence of an acid binder.Suitable acid binders for carrying out process P1 according to theinvention are in each case all inorganic and organic bases that arecustomary for such reactions. Preference is given to using alkalineearth metal, alkali metal hydride, alkali metal hydroxides or alkalimetal alkoxides, such as sodium hydroxide, sodium hydride, calciumhydroxide, potassium hydroxide, potassium tert-butoxide or otherammonium hydroxide, alkali metal carbonates, such as cesium carbonate,sodium carbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate, alkali metal or alkaline earth metal acetates, such assodium acetate, potassium acetate, calcium acetateand also tertiaryamines, such as trimethylamine, triethylamine, diisopropylethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an additional condensingagent or to employ an excess of the amine component, so that itsimultaneously acts as acid binder agent.

According to a further aspect according to the invention, there isprovided a process P2 for the preparation of carboxylic acid derivativesof formula (III) wherein T represents 0 and illustrated according to thefollowing reaction scheme:

wherein X² is as herein-defined;5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde is knownfrom WO-2004/014138 (reference example 35).

Step 1 of process P2 is performed in the presence of an oxidant, and ifappropriate in the presence of a solvent.

Steps 2 and 5 of process P2 are performed in the presence of acidhalide, and if appropriate in the presence of a solvent.

Step 3 of process P2 is performed in the presence of a fluorinatingagent, and if appropriate in the presence of a solvent.

Step 4 of process P2 is performed in the presence of an acid or a baseand if appropriate in the presence of a solvent

Suitable oxidants for carrying out step 1 of process P2 according to theinvention are in each case all inorganic and organic oxidant which arecustomary for such reactions. Preference is given to usingbenzyltriethylammonium permanganate, bromine, chlorine,m-chloroperbenzoic acid, chromic acid, chromium (VI) oxide, hydrogenperoxide, hydrogen peroxide-boron trifluoride, hydrogen peroxide-urea,2-hydroxyperoxyhexafluoro-2-propanol; Iodine, oxygen-platinum catalyst,perbenzoic acid, peroxyacetyl nitrate, potassium permanganate, potassiumruthenate, pyridinium dichromate, ruthenium (VIII) oxide, silver (I)oxide, silver (II) oxide, silver nitrite, sodium chlorite, sodiumhypochlorite, or 2,2,6,6-tetramethylpiperidin-1-oxyl.

Suitable acid halides for carrying out steps 2 and 5 of process P2according to the invention are in each case all organic or inorganicacid halides which are customary for such reactions. Preference is givento using notably phosgene, phosphorous trichloride, phosphorouspentachloride, phosphorous trichloride oxide, thionyl chloride, orcarbon tetrachloride-triphenylphosphine.

Suitable fluorinating agent for carrying out step 3 of process P2according to the invention is in each case all fluorinating agents whichare customary for such reactions. Preference is given to using cesiumfluoride, potassium fluoride, potassium fluoride-calcium difluoride, ortetrabutylammonium fluoride.

When carrying out steps 1 to 5 of process P2 according to the invention,the reaction temperatures can independently be varied within arelatively wide range. Generally, processes according to the inventionare carried out at temperatures between 0° C. and 160° C., preferablybetween 10° C. and 120° C. A way to control the temperature for theprocesses according to the invention is the use the micro-wavestechnology.

Steps 1 to 5 of process P2 according to the invention are generallyindependently carried out under atmospheric pressure. However, in eachcase, it is also possible to operate under elevated or reduced pressure.

When carrying out step 1 of process P2 according to the invention,generally one mole or excess amount of the oxidant is employed per moleof aldehyde of formula (IV). It is also possible to employ the reactioncomponents in other ratios.

When carrying out carrying out steps 2 and 5 of process P2 to theinvention, generally one mole or excess amount of the acid halides isemployed per mole of acid of formula (IIIa) or (IIId). It is alsopossible to employ the reaction components in other ratios.

When carrying out steps 3 of process P2 according to the inventiongenerally one mole or excess amount of fluorinating agent is employedper mole of acid chloride (IIIb). It is also possible to employ thereaction components in other ratios.

When carrying out steps 4 of process P2 according to the inventiongenerally one mole or excess amount of acid or base is employed per moleof acid fluoride (IIIc). It is also possible to employ the reactioncomponents in other ratios.

According to a further aspect according to the invention, there isprovided a process P3 for the preparation of a compound of formula (I)wherein T represents S, starting from a compound of formula (I) whereinT represents O and illustrated according to the following reactionscheme:

wherein X¹, X², Z¹, Z², Z³, n, Q¹ and B are as herein-defined, in theoptional presence of a catalytic or stoichiometric or excess amount,quantity of a base such as an inorganic and organic base. Preference isgiven to using alkali metal carbonates, such as sodium carbonate,potassium carbonate, potassium bicarbonate, sodium bicarbonate;heterocyclic aromatic bases, such as pyridine, picoline, lutidine,collidine; and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylaminopyridine or N-methyl-piperidine.

Process P3 according to the invention is performed in the presence of athionating agent.

Starting amide derivatives of formula (I) can be prepared according toprocesses P1.

Suitable thionating agents for carrying out process P3 according to theinvention can be sulfur (S), sulfhydric acid (H₂S), sodium sulfide(Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃),bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S),phosphorous pentasulfide (P₂S₅), Lawesson's reagent(2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) ora polymer-supported thionating reagent such as described in Journal ofthe Chemical Society, Perkin 1 (2001), 358.

Work-up is carried out by customary methods. Generally, the reactionmixture is treated with water and the organic phase is separated offand, after drying, concentrated under reduced pressure. If appropriate,the remaining residue can, be freed by customary methods, such aschromatography, recrystallization or distillation, from any impuritiesthat may still be present.

The compound according to the present invention can be preparedaccording to the general processes of preparation described above. Itwill nevertheless be understood that, on the basis of his generalknowledge and of available publications, the skilled worker will be ableto adapt this method according to the specifics of each of thecompounds, which it is desired to synthesize.

In a further aspect, the present invention also relates to a fungicidecomposition comprising an effective and non-phytotoxic amount of anactive compound of formula (I).

The expression “effective and non-phytotoxic amount” means an amount ofcomposition according to the invention that is sufficient to control ordestroy the fungi present or liable to appear on the cropsand that doesnot entail any appreciable symptom of phytotoxicity for the said crops.Such an amount can vary within a wide range depending on the fungus tobe controlled, the type of crop, the climatic conditions and thecompounds included in the fungicide composition according to theinvention. This amount can be determined by systematic field trials thatare within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicidecomposition comprising, as an active ingredient, an effective amount ofa compound of formula (I) as herein defined and an agriculturallyacceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural orsynthetic, organic or inorganic compound with that the active compoundof formula (I) is combined or associated to make it easier to apply,notably to the parts of the plant. This support is thus generally inertand should be agriculturally acceptable. The support can be a solid or aliquid. Examples of suitable supports include clays, natural orsynthetic silicates, silica, resins, waxes, solid fertilisers, water,alcohols, in particular butanol, organic solvents, mineral and plantoils and derivatives thereof. Mixtures of such supports can also beused.

The composition according to the invention can also comprise additionalcomponents. In particular, the composition can further comprise asurfactant. The surfactant can be an emulsifier, a dispersing agent or awetting agent of ionic or non-ionic type or a mixture of suchsurfactants. Mention can be made, for example, of polyacrylic acidsalts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonicacid salts, polycondensates of ethylene oxide with fatty alcohols orwith fatty acids or with fatty amines, substituted phenols (inparticular alkylphenols or arylphenols), salts of sulfosuccinic acidesters, taurine derivatives (in particular alkyl taurates), phosphoricesters of polyoxyethylated alcohols or phenols, fatty acid esters ofpolyolsand derivatives of the above compounds containing sulfate,sulfonate and phosphate functions. The presence of at least onesurfactant is generally essential when the active compound and/or theinert support are water-insoluble and when the vector agent for theapplication is water. Preferably, surfactant content can be comprisedfrom 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protectivecolloids, adhesives, thickeners, thixotropic agents, penetration agents,stabilisers, sequestering agents. More generally, the active compoundscan be combined with any solid or liquid additive, that complies withthe usual formulation techniques.

In general, the composition according to the invention can contain from0.05 to 99% by weight of active compound, preferably 10 to 70% byweight.

Compositions according to the invention can be used in various formssuch as aerosol dispenser, capsule suspension, cold fogging concentrate,dustable powder, emulsifiable concentrate, emulsion oil in water,emulsion water in oil, encapsulated granule, fine granule, flowableconcentrate for seed treatment, gas (under pressure), gas generatingproduct, granule, hot fogging concentrate, macrogranule, microgranule,oil dispersible powder, oil miscible flowable concentrate, oil miscibleliquid, paste, plant rodlet, powder for dry seed treatment, seed coatedwith a pesticide, soluble concentrate, soluble powder, solution for seedtreatment, suspension concentrate (flowable concentrate), ultra lowvolume (ULV) liquid, ultra low volume (ULV) suspension, waterdispersible granules or tablets, water dispersible powder for slurrytreatment, water soluble granules or tablets, water soluble powder forseed treatment and wettable powder. These compositions include not onlycompositions that are ready to be applied to the plant or seed to betreated by means of a suitable device, such as a spraying or dustingdevice, but also concentrated commercial compositions that must bediluted before application to the crop.

The compounds according to the invention can also be mixed with one ormore insecticide, fungicide, bactericide, attractant, acaricide orpheromone active substance or other compounds with biological activity.The mixtures thus obtained have normally a broadened spectrum ofactivity. The mixtures with other fungicide compounds are particularlyadvantageous.

Examples of suitable fungicide mixing partners can be selected in thefollowing lists:

(1) Inhibitors of the ergosterol biosynthesis, for example (1.1)aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol(55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole(113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole(119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M(83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate(31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole(60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole(114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin(67306-00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole(136426-54-5), (1.20) flurprimidol (56425-91-3), (1.21) flusilazole(85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazole(112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole(79983-71-4), (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate(58594-72-2), (1.28) imibenconazole (86598-92-7), (1.29) ipconazole(125225-28-7), (1.30) metconazole (125116-23-6), (1.31) myclobutanil(88671-89-0), (1.32) naftifine (65472-88-0), (1.33) nuarimol(63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol(76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazole(66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz(67747-09-5), (1.40) propiconazole (60207-90-1), (1.41) prothioconazole(178928-70-6), (1.42) pyributicarb (88678-67-5), (1.43) pyrifenox(88283-41-4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole(149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole(107534-96-3), (1.48) terbinafine (91161-71-6), (1.49) tetraconazole(112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol(89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole(68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole(131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p(83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole(137234-62-9), (1.60)1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol (129586-32-9),(1.61) methyl1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate(110323-95-0), (1.62)N′-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide,(1.63)N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamideand (1.64)O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl]1H-imidazole-1-carbothioate(111226-71-2).(2) inhibitors of the respiratory chain at complex I or II, for example(2.1) bixafen (581809-46-3), (2.2) boscalid (188425-85-6), (2.3)carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5) fenfuram(24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil(66332-96-5), (2.8) fluxapyroxad (907204-31-3), (2.9) furametpyr(123572-88-3), (2.10) furmecyclox (60568-05-0), (2.11) isopyrazam(mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate1RS,4SR,9SR) (881685-58-1), (2.12) isopyrazam (anti-epimeric racemate1RS,4SR,9SR), (2.13) isopyrazam (anti-epimeric enantiomer 1R,4S,9S),(2.14) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.15) isopyrazam(syn epimeric racemate 1RS,4SR,9RS), (2.16) isopyrazam (syn-epimericenantiomer 1R,4S,9R), (2.17) isopyrazam (syn-epimeric enantiomer1S,4R,9S), (2.18) mepronil (55814-41-0), (2.19) oxycarboxin (5259-88-1),(2.20) penflufen (494793-67-8), (2.21) penthiopyrad (183675-82-3),(2.22) sedaxane (874967-67-6), (2.23) thifluzamide (130000-40-7), (2.24)1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,(2.25)3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,(2.26)3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide,(2.27)N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(1092400-95-7) (WO 2008148570), (2.28)5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine(1210070-84-0) (WO2010025451), (2.29)N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,(2.30)N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamideand (2.31)N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.(3) inhibitors of the respiratory chain at complex III, for example(3.1) ametoctradin (865318-97-4), (3.2) amisulbrom (348635-87-0), (3.3)azoxystrobin (131860-33-8), (3.4) cyazofamid (120116-88-3), (3.5)coumethoxystrobin (850881-30-0), (3.6) coumoxystrobin (850881-70-8),(3.7) dimoxystrobin (141600-52-4), (3.8) enestroburin (238410-11-2) (WO2004/058723), (3.9) famoxadone (131807-57-3) (WO 2004/058723), (3.10)fenamidone (161326-34-7) (WO 2004/058723), (3.11) fenoxystrobin(918162-02-4), (3.12) fluoxastrobin (361377-29-9) (WO 2004/058723),(3.13) kresoxim-methyl (143390-89-0) (WO 2004/058723), (3.14)metominostrobin (133408-50-1) (WO 2004/058723), (3.15) orysastrobin(189892-69-1) (WO 2004/058723), (3.16) picoxystrobin (117428-22-5) (WO2004/058723), (3.17) pyraclostrobin (175013-18-0) (WO 2004/058723),(3.18) pyrametostrobin (915410-70-7) (WO 2004/058723), (3.19)pyraoxystrobin (862588-11-2) (WO 2004/058723), (3.20) pyribencarb(799247-52-2) (WO 2004/058723), (3.21) triclopyricarb (902760-40-1),(3.22) trifloxystrobin (141517-21-7) (WO 2004/058723), (3.23)(2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide(WO 2004/058723), (3.24)(2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide(WO 2004/058723), (3.25)(2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide(158169-73-4), (3.26)(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide(326896-28-0), (3.27)(2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide,(3.28)2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide(119899-14-8), (3.29)5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one,(3.30) methyl(2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxyprop-2-enoate(149601-03-6), (3.31)N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide(226551-21-9), (3.32)2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide(173662-97-0) and (3.33)(2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide(394657-24-0).(4) Inhibitors of the mitosis and cell division, for example (4.1)benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3)chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5)ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7)fuberidazole (3878-19-1), (4.8) pencycuron (66063-05-6), (4.9)thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11)thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13)5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine(214706-53-3) and (4.14)3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(1002756-87-7).(5) Compounds capable to have a multisite action, like for example (5.1)bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1), (5.3) captan(133-06-2) (WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copperhydroxide (20427-59-2), (5.6) copper naphthenate (1338-02-9), (5.7)copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9)copper(2+) sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11)dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine freebase, (5.14) ferbam (14484-64-1), (5.15) fluorofolpet (719-96-0), (5.16)folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatineacetate, (5.19) iminoctadine (13516-27-3), (5.20) iminoctadinealbesilate (169202-06-6), (5.21) iminoctadine triacetate (57520-17-9),(5.22) mancopper (53988-93-5), (5.23) mancozeb (8018-01-7), (5.24) maneb(12427-38-2), (5.25) metiram (9006-42-2), (5.26) metiram zinc(9006-42-2), (5.27) oxine-copper (10380-28-6), (5.28) propamidine(104-32-5), (5.29) propineb (12071-83-9), (5.30) sulfur and sulfurpreparations including calcium polysulfide (7704-34-9), (5.31) thiram(137-26-8), (5.32) tolylfluanid (731-27-1), (5.33) zineb (12122-67-7)and (5.34) ziram (137-30-4).(6) Compounds capable to induce a host defence, for example (6.1)acibenzolar-S-methyl (135158-54-2), (6.2) isotianil (224049-04-1), (6.3)probenazole (27605-76-1) and (6.4) tiadinil (223580-51-6).(7) Inhibitors of the amino acid and/or protein biosynthesis, forexample (7.1) andoprim (23951-85-1), (7.2) blasticidin-S (2079-00-7),(7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980-18-3), (7.5)kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim(110235-47-7), (7.7) pyrimethanil (53112-28-0) and (7.8)3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline(861647-32-7) (WO2005070917).(8) Inhibitors of the ATP production, for example (8.1) fentin acetate(900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide(76-87-9) and (8.4) silthiofam (175217-20-6).(9) Inhibitors of the cell wall synthesis, for example (9.1)benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3)flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5)mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7)polyoxorim (22976-86-9), (9.8) validamycin A (37248-47-8) and (9.9)valifenalate (283159-94-4; 283159-90-0).(10) Inhibitors of the lipid and membrane synthesis, for example (10.1)biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran(99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole(2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos(26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb(25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11)prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18-6), (10.13)quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15)tolclofos-methyl (57018-04-9).(11) Inhibitors of the melanine biosynthesis, for example (11.1)carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3)fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5)pyroquilon (57369-32-1), (11.6) tricyclazole (41814-78-2) and (11.7)2,2,2-trifluoroethyl{3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate (851524-22-6)(WO2005042474).(12) Inhibitors of the nucleic acid synthesis, for example (12.1)benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5),(12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8), (12.5)dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7)furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9) metalaxyl(57837-19-1), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11)ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinicacid (14698-29-4).(13) Inhibitors of the signal transduction, for example (13.1)chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3)fludioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5)procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7)vinclozolin (50471-44-8).(14) Compounds capable to act as an uncoupler, for example (14.1)binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone(89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptyldinocap(131-72-6).(15) Further compounds, for example (15.1) benthiazole (21564-17-0),(15.2) bethoxazin (163269-30-5), (15.3) capsimycin (70694-08-5), (15.4)carvone (99-49-0), (15.5) chinomethionat (2439-01-2), (15.6) pyriofenone(chlazafenone) (688046-61-9), (15.7) cufraneb (11096-18-7), (15.8)cyflufenamid (180409-60-3), (15.9) cymoxanil (57966-95-7), (15.10)cyprosulfamide (221667-31-8), (15.11) dazomet (533-74-4), (15.12)debacarb (62732-91-6), (15.13) dichlorophen (97-23-4), (15.14)diclomezine (62865-36-5), (15.15) difenzoquat (49866-87-7), (15.16)difenzoquat methylsulfate (43222-48-6), (15.17) diphenylamine(122-39-4), (15.18) ecomate, (15.19) fenpyrazamine (473798-59-3),(15.20) flumetover (154025-04-4), (15.21) fluoroimide (41205-21-4),(15.22) flusulfamide (106917-52-6), (15.23) flutianil (304900-25-2),(15.24) fosetyl-aluminium (39148-24-8), (15.25) fosetyl-calcium, (15.26)fosetyl-sodium (39148-16-8), (15.27) hexachlorobenzene (118-74-1),(15.28) irumamycin (81604-73-1), (15.29) methasulfocarb (66952-49-6),(15.30) methyl isothiocyanate (556-61-6), (15.31) metrafenone(220899-03-6), (15.32) mildiomycin (67527-71-3), (15.33) natamycin(7681-93-8), (15.34) nickel dimethyldithiocarbamate (15521-65-0),(15.35) nitrothal-isopropyl (10552-74-6), (15.36) octhilinone(26530-20-1), (15.37) oxamocarb (917242-12-7), (15.38) oxyfenthiin(34407-87-9), (15.39) pentachlorophenol and salts (87-86-5), (15.40)phenothrin, (15.41) phosphorous acid and its salts (13598-36-2), (15.42)propamocarb-fosetylate, (15.43) propanosine-sodium (88498-02-6), (15.44)proquinazid (189278-12-4), (15.45) pyrimorph (868390-90-3), (15.45e)(2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one(1231776-28-5), (15.45z)(2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one(1231776-29-6), (15.46) pyrrolnitrine (1018-71-9) (EP-A 1 559 320),(15.47) tebufloquin (376645-78-2), (15.48) tecloftalam (76280-91-6),(15.49) tolnifanide (304911-98-6), (15.50) triazoxide (72459-58-6),(15.51) trichlamide (70193-21-4), (15.52) zarilamid (84527-51-5),(15.53)(3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl2-methylpropanoate (517875-34-2) (WO2003035617), (15.54)1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(1003319-79-6) (WO 2008013622), (15.55)1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(1003319-80-9) (WO 2008013622), (15.56)1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(1003318-67-9) (WO 2008013622), (15.57)1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl 1H-imidazole-1-carboxylate(111227-17-9), (15.58) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine(13108-52-6), (15.59)2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7),(15.60)2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,(15.61)2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(1003316-53-7) (WO 2008013622), (15.62)2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5S)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(1003316-54-8) (WO 2008013622), (15.63)2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1,2-oxazol-3-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(1003316-51-5) (WO 2008013622), (15.64)2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.65)2-chloro-5-[2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl]pyridine,(15.66) 2-phenylphenol and salts (90-43-7), (15.67)3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline(861647-85-0) (WO2005070917), (15.68)3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.69)3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine, (15.70)3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine,(15.71)4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine,(15.72) 5-amino-1,3,4-thiadiazole-2-thiol, (15.73)5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide(134-31-6), (15.74) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine(1174376-11-4) (WO2009094442), (15.75)5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine (1174376-25-0)(WO2009094442), (15.76)5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.77) ethyl(2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.78)N′-(4-{[3-(4-chlorobenzyl)-1,2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide,(15.79)N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,(15.80)N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,(15.81)N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide,(15.82)N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide,(15.83)N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide,(15.84)N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide(221201-92-9), (15.85)N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide(221201-92-9), (15.86)N′-{4-[(3-tert-butyl-4-cyano-1,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl}-N-ethyl-N-methylimidoformamide,(15.87)N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide(922514-49-6) (WO 2007014290), (15.88)N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide(922514-07-6) (WO 2007014290), (15.89)N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1S)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide(922514-48-5) (WO 2007014290), (15.90) pentyl{6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate,(15.91) phenazine-1-carboxylic acid, (15.92) quinolin-8-ol (134-31-6),(15.93) quinolin-8-ol sulfate (2:1) (134-31-6) and (15.94) tert-butyl{6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.(16) Further compounds, for example (16.1)1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide,(16.2)N-(4′-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,(16.3)N-(2′,4′-dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,(16.4)3-(difluoromethyl)-1-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide,(16.5)N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,(16.6)3-(difluoromethyl)-1-methyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.7)5-fluoro-1,3-dimethyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.8)2-chloro-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide(known from WO 2004/058723), (16.9)3-(difluoromethyl)-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.10)N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.11)3-(difluoromethyl)-N-(4′-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.12)N-(4′-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.13)2-chloro-N-(4′-ethynylbiphenyl-2-yl)pyridine-3-carboxamide (known fromWO 2004/058723), (16.14)2-chloro-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide(known from WO 2004/058723), (16.15)4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1,3-thiazole-5-carboxamide(known from WO 2004/058723), (16.16)5-fluoro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.17)2-chloro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide(known from WO 2004/058723), (16.18)3-(difluoromethyl)-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.19)5-fluoro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide(known from WO 2004/058723), (16.20)2-chloro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide(known from WO 2004/058723), (16.21)(5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone(known from EP-A 1 559 320), (16.22)N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamide(220706-93-4), (16.23) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid and(16.24) but-3-yn-1-yl{6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.

All named mixing partners of the classes (1) to (16) can, if theirfunctional groups enable this, optionally form salts with suitable basesor acids.

The composition according to the invention comprising a mixture of acompound of formula (I) with a bactericide compound can also beparticularly advantageous. Examples of suitable bactericide mixingpartners can be selected in the following list: bronopol, dichlorophen,nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone,furancarboxylic acid, oxytetracycline, probenazole, streptomycin,tecloftalam, copper sulfate and other copper preparations.

The compounds of formula (I) and the fungicide composition according tothe invention can be used to curatively or preventively control thephytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provideda method for curatively or preventively controlling the phytopathogenicfungi of plants or crops characterised in that a compound of formula (I)or a fungicide composition according to the invention is applied to theseed, the plant or to the fruit of the plant or to the soil wherein theplant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful totreat propagation material such as tubers or rhizomes, but also seeds,seedlings or seedlings pricking out and plants or plants pricking out.This method of treatment can also be useful to treat roots. The methodof treatment according to the invention can also be useful to treat theoverground parts of the plant such as trunks, stems or stalks, leaves,flowers and fruit of the concerned plant.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to theinvention, mention may be made of major field crops like corn, soybean,cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassicarapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat,sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vineand various fruits and vegetables of various botanical taxa such asRosaceae sp. (for instance pip fruit such as apples and pears, but alsostone fruit such as apricots, cherries, almonds and peaches, berryfruits such as strawberries), Ribesioidae sp., Juglandaceae sp.,Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceaesp., Actimidaceae sp., Lauraceae sp., Musaceae sp. (for instance bananatrees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp.,Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges andgrapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers,eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce,artichoke and chicory—including root chicory, endive or common chicory),Umbelliferae sp. (for instance carrot, parsley, celery and celeriac),Cucurbitaceae sp. (for instance cucumber—including pickling cucumber,squash, watermelon, gourds and melons), Alliaceae sp. (for instanceonions and leek), Cruciferae sp. (for instance white cabbage, redcabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi,radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (forinstance peanuts, peas and beans beans—such as climbing beans and broadbeans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach,beetroots), Malvaceae (for instance okra), Asparagaceae (for instanceasparagus); horticultural and forest crops; ornamental plants; as wellas genetically modified homologues of these crops.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology or RNAinterference—RNAi—technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in additionaleffects. Thus, for example, reduced application rates and/or a wideningof the activity spectrum and/or an increase in the activity of theactive compounds and compositions which can be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, bigger fruits, larger plant height,greener leaf color, earlier flowering, higher quality and/or a highernutritional value of the harvested products, higher sugar concentrationwithin the fruits, better storage stability and/or processability of theharvested products are possible, which exceed the effects which wereactually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted microorganisms. This may, ifappropriate, be one of the reasons of the enhanced activity of thecombinations according to the invention, for example against fungi.Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances orcombinations of substances which are capable of stimulating the defensesystem of plants in such a way that, when subsequently inoculated withunwanted microorganisms, the treated plants display a substantial degreeof resistance to these microorganisms. In the present case, unwantedmicroorganisms are to be understood as meaning phytopathogenic fungi,bacteria and viruses. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patentapplication Ser. Nos 11/765,491, 11/765,494, 10/926,819, 10/782,020,12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808,12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335,11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Examples of plants with the above-mentioned traits are non-exhaustivelylisted in Table A.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396 in which, forexample, a ribonuclease such as barnase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Comai et al., 1983,Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.(Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genesencoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), aTomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or anEleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS asdescribed in for example EP 0837944, WO 00/66746, WO 00/66747 orWO02/26995. Glyphosate-tolerant plants can also be obtained byexpressing a gene that encodes a glyphosate oxido-reductase enzyme asdescribed in U.S. Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerantplants can also be obtained by expressing a gene that encodes aglyphosate acetyl transferase enzyme as described in for example WO02/36782, WO 03/092360, WO 05/012515 and WO 07/024,782.Glyphosate-tolerant plants can also be obtained by selecting plantscontaining naturally-occurring mutations of the above-mentioned genes,as described in for example WO 01/024615 or WO 03/013226. Plantsexpressing EPSPS genes that confer glyphosate tolerance are described ine.g. U.S. patent application Ser. Nos 11/517,991, 10/739,610,12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598,11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526,11/769,327, 11/769,255, 11/943,801 or 12/362,774. Plants comprisingother genes that confer glyphosate tolerance, such as decarboxylasegenes, are described in e.g. U.S. patent application Ser. Nos.11/588,811, 11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition, e.g. described in U.S.patent application Ser. No. 11/760,602. One such efficient detoxifyingenzyme is an enzyme encoding a phosphinothricin acetyltransferase (suchas the bar or pat protein from Streptomyces species). Plants expressingan exogenous phosphinothricin acetyltransferase are for exampledescribed in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894;5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD-inhibitors can be transformedwith a gene encoding a naturally-occurring resistant HPPD enzyme, or agene encoding a mutated or chimeric HPPD enzyme as described in WO96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, orU.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitors can also beobtained by transforming plants with genes encoding certain enzymesenabling the formation of homogentisate despite the inhibition of thenative HPPD enzyme by the HPPD-inhibitor. Such plants and genes aredescribed in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPDinhibitors can also be improved by transforming plants with a geneencoding an enzyme having prephenate deshydrogenase (PDH) activity inaddition to a gene encoding an HPPD-tolerant enzyme, as described in WO2004/024928. Further, plants can be made more tolerant to HPPD-inhibitorherbicides by adding into their genome a gene encoding an enzyme capableof metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymesshown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and international publication WO 96/33270. Other imidazolinone-tolerantplants are also described in for example WO 2004/040012, WO 2004/106529,WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO2006/024351, and WO 2006/060634. Further sulfonylurea- andimidazolinone-tolerant plants are also described in for example WO07/024,782 and U.S. Patent Application No. 61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis        or an insecticidal portion thereof, such as the insecticidal        crystal proteins listed by Crickmore et al. (1998, Microbiology        and Molecular Biology Reviews, 62: 807-813), updated by        Crickmore et al. (2005) at the Bacillus thuringiensis toxin        nomenclature, online at:        http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or        insecticidal portions thereof, e.g., proteins of the Cry protein        classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab,        Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP        1999141 and WO 2007/107302), or such proteins encoded by        synthetic genes as e.g. described in and U.S. patent application        Ser. No. 12/249,016; or    -   2) a crystal protein from Bacillus thuringiensis or a portion        thereof which is insecticidal in the presence of a second other        crystal protein from Bacillus thuringiensis or a portion        thereof, such as the binary toxin made up of the Cry34 and Cry35        crystal proteins (Moellenbeck et al. 2001, Nat. Biotechnol. 19:        668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71,        1765-1774) or the binary toxin made up of the Cry1A or Cry1F        proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5); or    -   3) a hybrid insecticidal protein comprising parts of different        insecticidal crystal proteins from Bacillus thuringiensis, such        as a hybrid of the proteins of 1) above or a hybrid of the        proteins of 2) above, e.g., the Cry1A.105 protein produced by        corn event MON89034 (WO 2007/027777); or    -   4) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation, such as the        Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A        protein in corn event MIR604; or    -   5) an insecticidal secreted protein from Bacillus thuringiensis        or Bacillus cereus, or an insecticidal portion thereof, such as        the vegetative insecticidal (VIP) proteins listed at:        http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,        e.g., proteins from the VIP3Aa protein class; or    -   6) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a second        secreted protein from Bacillus thuringiensis or B. cereus, such        as the binary toxin made up of the VIP1A and VIP2A proteins (WO        94/21795); or    -   7) a hybrid insecticidal protein comprising parts from different        secreted proteins from Bacillus thuringiensis or Bacillus        cereus, such as a hybrid of the proteins in 1) above or a hybrid        of the proteins in 2) above; or    -   8) a protein of any one of 5) to 7) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation (while still        encoding an insecticidal protein), such as the VIP3Aa protein in        cotton event COT102; or    -   9) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a crystal        protein from Bacillus thuringiensis, such as the binary toxin        made up of VIP3 and Cry1A or Cry1F (U.S. Patent Appl. No.        61/126,083 and 61/195,019), or the binary toxin made up of the        VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5).    -   10) a protein of 9) above wherein some, particularly 1 to 10,        amino acids have been replaced by another amino acid to obtain a        higher insecticidal activity to a target insect species, and/or        to expand the range of target insect species affected, and/or        because of changes introduced into the encoding DNA during        cloning or transformation (while still encoding an insecticidal        protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest, asdescribed e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   -   1) plants which contain a transgene capable of reducing the        expression and/or the activity of poly(ADP-ribose) polymerase        (PARP) gene in the plant cells or plants as described in WO        00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.    -   2) plants which contain a stress tolerance enhancing transgene        capable of reducing the expression and/or the activity of the        PARG encoding genes of the plants or plants cells, as described        e.g. in WO 2004/090140.    -   3) plants which contain a stress tolerance enhancing transgene        coding for a plant-functional enzyme of the nicotineamide        adenine dinucleotide salvage synthesis pathway including        nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic        acid mononucleotide adenyl transferase, nicotinamide adenine        dinucleotide synthetase or nicotine amide        phosphorybosyltransferase as described e.g. in EP 04077624.7, WO        2006/133827, PCT/EP07/002,433, EP 1999263, or WO 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which        in its physical-chemical characteristics, in particular the        amylose content or the amylose/amylopectin ratio, the degree of        branching, the average chain length, the side chain        distribution, the viscosity behaviour, the gelling strength, the        starch grain size and/or the starch grain morphology, is changed        in comparison with the synthesised starch in wild type plant        cells or plants, so that this is better suited for special        applications. Said transgenic plants synthesizing a modified        starch are disclosed, for example, in EP 0571427, WO 95/04826,        EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188,        WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545,        WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654,        WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229,        WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO        2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO        2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO        2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO        00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP        06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP        07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO        2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145,        WO 99/12950, WO 99/66050, WO 99/53072, U.S. Pat. No. 6,734,341,        WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509,        WO 2005/002359, U.S. Pat. No. 5,824,790, U.S. Pat. No.        6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026,        WO 97/20936    -   2) transgenic plants which synthesize non starch carbohydrate        polymers or which synthesize non starch carbohydrate polymers        with altered properties in comparison to wild type plants        without genetic modification. Examples are plants producing        polyfructose, especially of the inulin and levan-type, as        disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460,        and WO 99/24593, plants producing alpha-1,4-glucans as disclosed        in WO 95/31553, US 2002031826, U.S. Pat. No. 6,284,479, U.S.        Pat. No. 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO        00/14249, plants producing alpha-1,6 branched alpha-1,4-glucans,        as disclosed in WO 00/73422, plants producing alternan, as        disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, U.S.        Pat. No. 5,908,975 and EP 0728213,    -   3) transgenic plants which produce hyaluronan, as for example        disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO        2007/039316, JP 2006304779, and WO 2005/012529.    -   4) transgenic plants or hybrid plants, such as onions with        characteristics such as ‘high soluble solids content’, ‘low        pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.        patent application Ser. No. 12/020,360 and 61/054,026.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of        cellulose synthase genes as described in WO 98/00549    -   b) Plants, such as cotton plants, containing an altered form of        rsw2 or rsw3 homologous nucleic acids as described in WO        2004/053219    -   c) Plants, such as cotton plants, with increased expression of        sucrose phosphate synthase as described in WO 01/17333    -   d) Plants, such as cotton plants, with increased expression of        sucrose synthase as described in WO 02/45485    -   e) Plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fiber cell is altered,        e.g. through downregulation of fiber-selective β-1,3-glucanase        as described in WO 2005/017157, or as described in EP 08075514.3        or U.S. Patent Appl. No. 61/128,938    -   f) Plants, such as cotton plants, having fibers with altered        reactivity, e.g. through the expression of        N-acetylglucosaminetransferase gene including nodC and chitin        synthase genes as described in WO 2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a        high oleic acid content as described e.g. in U.S. Pat. No.        5,969,169, U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or        U.S. Pat. No. 6,063,947    -   b) Plants such as oilseed rape plants, producing oil having a        low linolenic acid content as described in U.S. Pat. No.        6,270,828, U.S. Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755    -   c) Plant such as oilseed rape plants, producing oil having a low        level of saturated fatty acids as described e.g. in U.S. Pat.        No. 5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering as described in U.S. Patent Appl. No. 61/135,230 WO09/068,313and WO10/006,732.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor non-regulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road Riverdale, Md. 20737, USA), for instance onits internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). Onthe filing date of this application the petitions for nonregulatedstatus that were pending with APHIS or granted by APHIS were thoselisted in table B which contains the following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

Further particularly transgenic plants include plants containing atransgene in an agronomically neutral or beneficial position asdescribed in any of the patent publications listed in Table C.

TABLE A Trait Reference Water use efficiency WO 2000/073475 Nitrogen useefficiency WO 1995/009911 WO 2007/076115 WO 1997/030163 WO 2005/103270WO 2007/092704 WO 2002/002776 Improved photosynthesis WO 2008/056915 WO2004/101751 Nematode resistance WO 1995/020669 WO 2003/033651 WO2001/051627 WO 1999/060141 WO 2008/139334 WO 1998/012335 WO 2008/095972WO 1996/030517 WO 2006/085966 WO 1993/018170 Reduced pod dehiscence WO2006/009649 WO 1997/013865 WO 2004/113542 WO 1996/030529 WO 1999/015680WO 1994/023043 WO 1999/000502 Aphid resistance WO 2006/125065 WO2008/067043 WO 1997/046080 WO 2004/072109 Sclerotinia resistance WO2006/135717 WO 2005/000007 WO 2006/055851 WO 2002/099385 WO 2005/090578WO 2002/061043 Botrytis resistance WO 2006/046861 WO 2002/085105 Bremiaresistance US 20070022496 WO 2004/049786 WO 2000/063432 Erwiniaresistance WO 2004/049786 Closterovirus resistance WO 2007/073167 WO2002/022836 WO 2007/053015 Stress tolerance (including WO 2010/019838WO2008/002480 drought tolerance) WO 2009/049110 WO2005/033318Tobamovirus resistance WO 2006/038794

TABLE B Petitions of Nonregulated Status Granted or Pending by APHIS asof Mar. 31, 2010 Applicant Documents Extension of Petition RegulatedTransgenic Transformation Petition Number *** Institution ArticlePhenotype Event or Line Petitions for Nonregulated Status Pending10-070-01p Virginia Tech Peanut Sclerotinia blight N70, P39, andresistant W171 09-349-01p Dow Soybean Herbicide Tolerant DAS-68416-4AgroSciences 09-328-01p Bayer Crop Soybean Herbicide Tolerant FG72Science 09-233-01p Dow Corn Herbicide Tolerant DAS-40278-9 09-201-01pMonsanto Soybean MON-877Ø5-6 09-183-01p Monsanto Soybean MON-8776909-082-01p Monsanto Soybean Lepidopteran resistant MON 87701 09-063-01pStine Seed Corn Glyphosate tolerant HCEM485 09-055-01p Monsanto CornDrought Tolerant MON 87460 09-015-01p BASF Plant Soybean HerbicideTolerant BPS-CV127-9 Science, LLC Soybean 08-366-01p ArborGen EucalyptusFreeze Tolerant, ARB-FTE1-08 Fertility Altered 08-340-01p Bayer CottonGlufosinate Tolerant, T304-40XGHB119 Insect Resistant 08-338-01p PioneerCorn Male Sterile, Fertility DP-32138-1 Restored, Visual Marker08-315-01p Florigene Rose Altered Flower Color IFD-524Ø1-4 andIFD-529Ø1-9 07-253-01p Syngenta Corn Lepidopteran resistant MIR-162Maize 07-108-01p Syngenta Cotton Lepidopteran Resistant COT67B06-354-01p Pioneer Soybean High Oleic Acid DP-3Ø5423-1 05-280-01pSyngenta Corn Thermostable alpha- 3272 amylase 04-110-01p Monsanto &Alfalfa Glyphosate Tolerant J101, J163 Forage Genetics 03-104-01pMonsanto & Creeping Glyphosate Tolerant ASR368 Scotts bentgrassPetitions for Nonregulated Status Granted 07-152-01p Pioneer Cornglyphosate & DP-098140-6 Imidazolinone tolerant 04-337-01p University ofPapaya Papaya Ringspot Virus X17-2 Florida Resistant 06-332-01p BayerCotton Glyphosate tolerant GHB614 CropScience 06-298-01p Monsanto CornEuropean Corn Borer MON 89034 resistant 06-271-01p Pioneer SoybeanGlyphosate & 356043 acetolactate synthase (DP-356Ø43-5) tolerant06-234-01p 98-329-01p Bayer Rice Phosphinothricin LLRICE601 CropSciencetolerant 06-178-01p Monsanto Soybean Glyphosate tolerant MON 8978804-362-01p Syngenta Corn Corn Rootworm MIR604 Protected 04-264-01p ARSPlum Plum Pox Virus C5 Resistant 04-229-01p Monsanto Corn High LysineLY038 04-125-01p Monsanto Corn Corn Rootworm 88017 Resistant 04-086-01pMonsanto Cotton Glyphosate Tolerant MON 88913 03-353-01p Dow Corn CornRootworm 59122 Resistant 03-323-01p Monsanto Sugar Glyphosate TolerantH7-1 Beet 03-181-01p 00-136-01p Dow Corn Lepidopteran Resistant TC-6275& Phosphinothricin tolerant 03-155-01p Syngenta Cotton LepidopteranResistant COT 102 03-036-01p Mycogen/Dow Cotton Lepidopteran Resistant281-24-236 03-036-02p Mycogen/Dow Cotton Lepidopteran Resistant3006-210-23 02-042-01p Aventis Cotton Phosphinothericin LLCotton25tolerant 01-324-01p 98-216-01p Monsanto Rapeseed Glyphosate tolerantRT200 01-206-01p 98-278-01p Aventis Rapeseed Phosphinothricin MS1 &RF1/RF2 tolerant & pollination control 01-206-02p 97-205-01p AventisRapeseed Phosphinothricin Topas 19/2 tolerant 01-137-01p Monsanto CornCorn Rootworm MON 863 Resistant 01-121-01p Vector Tobacco Reducednicotine Vector 21-41 00-342-01p Monsanto Cotton Lepidopteran resistantCotton Event 15985 00-136-01p Mycogen c/o Corn Lepidopteran resistantLine 1507 Dow & Pioneer phosphinothricin tolerant 00-011-01p 97-099-01pMonsanto Corn Glyphosate tolerant NK603 99-173-01p 97-204-01p MonsantoPotato PLRV & CPB resistant RBMT22-82 98-349-01p 95-228-01p AgrEvo CornPhosphinothricin MS6 tolerant and Male sterile 98-335-01p U. of FlaxTolerant to soil CDC Triffid Saskatchewan residues of sulfonyl ureaherbicide 98-329-01p AgrEvo Rice Phosphinothricin LLRICE06, tolerantLLRICE62 98-278-01p AgrEvo Rapeseed Phosphinothricin MS8 & RF3 tolerant& Pollination control 98-238-01p AgrEvo Soybean Phosphinothricin GU262tolerant 98-216-01p Monsanto Rapeseed Glyphosate tolerant RT7398-173-01p Novartis Seeds & Beet Glyphosate tolerant GTSB77 Monsanto98-014-01p 96-068-01p AgrEvo Soybean Phosphinothricin A5547-127 tolerant97-342-01p Pioneer Corn Male sterile & 676, 678, 680 Phosphinothricintolerant 97-339-01p Monsanto Potato CPB & PVY resistant RBMT15-101,SEMT15-02, SEMT15-15 97-336-01p AgrEvo Beet Phosphinothricin T-120-7tolerant 97-287-01p Monsanto Tomato Lepidopteran resistant 534597-265-01p AgrEvo Corn Phosphinothricin CBH-351 tolerant & Lep.resistant 97-205-01p AgrEvo Rapeseed Phosphinothricin T45 tolerant97-204-01p Monsanto Potato CPB & PLRV resistant RBMT21-129 & RBMT21-35097-148-01p Bejo Cichorium Male sterile RM3-3, RM3-4, intybus RM3-697-099-01p Monsanto Corn Glyphosate tolerant GA21 97-013-01p CalgeneCotton Bromoxynil tolerant & Events 31807 & Lepidopteran resistant 3180897-008-01p Du Pont Soybean Oil profile altered G94-1, G94-19, G- 16896-317-01p Monsanto Corn Glyphosate tolerant & MON802 ECB resistant96-291-01p DeKalb Corn European Corn Borer DBT418 resistant 96-248-01p92-196-01p Calgene Tomato Fruit ripening altered 1 additional FLAVRSAVRline 96-068-01p AgrEvo Soybean Phosphinothricin W62, W98, A2704-tolerant 12, A2704-21, A5547-35 96-051-01p Cornell U Papaya PRSVresistant 55-1, 63-1 96-017-01p 95-093-01p Monsanto Corn European CornBorer MON809 & resistant MON810 95-352-01p Asgrow Squash CMV, ZYMV, WMV2CZW-3 resistant 95-338-01p Monsanto Potato CPB resistant SBT02-5 & -7,ATBT04-6 &-27, -30, -31, -36 95-324-01p Agritope Tomato Fruit ripeningaltered 35 1 N 95-256-01p Du Pont Cotton Sulfonylurea tolerant 19-51a95-228-01p Plant Genetic Corn Male sterile MS3 Systems 95-195-01pNorthrup King Corn European Corn Borer Bt11 resistant 95-179-01p92-196-01p Calgene Tomato Fruit ripening altered 2 additional FLAVRSAVRlines 95-145-01p DeKalb Corn Phosphinothricin B16 tolerant 95-093-01pMonsanto Corn Lepidopteran resistant MON 80100 95-053-01p MonsantoTomato Fruit ripening altered 8338 95-045-01p Monsanto Cotton Glyphosatetolerant 1445, 1698 95-030-01p 92-196-01p Calgene Tomato Fruit ripeningaltered 20 additional FLAVRSAVR lines 94-357-01p AgrEvo CornPhosphinothricin T14, T25 tolerant 94-319-01p Ciba Seeds CornLepidopteran resistant Event 176 94-308-01p Monsanto Cotton Lepidopteranresistant 531, 757, 1076 94-290-01p Zeneca & Tomato Fruitpolygalacturonase B, Da, F Petoseed level decreased 94-257-01p MonsantoPotato Coleopteran resistant BT6, BT10, BT12, BT16, BT17, BT18, BT2394-230-01p 92-196-01p Calgene Tomato Fruit ripening altered 9 additionalFLAVRSAVR lines 94-228-01p DNA Plant Tech Tomato Fruit ripening altered1345-4 94-227-01p 92-196-01p Calgene Tomato Fruit ripening altered LineN73 1436-111 94-090-01p Calgene Rapeseed Oil profile altered pCGN3828-212/86- 18 & 23 93-258-01p Monsanto Soybean Glyphosate tolerant 40-3-293-196-01p Calgene Cotton Bromoxynil tolerant BXN 92-204-01p UpjohnSquash WMV2 & ZYMV ZW-20 resistant 92-196-01p Calgene Tomato Fruitripening altered FLAVR SAVR NOTE: To obtain the most up-to-date list ofCrops No Longer Regulated, please look at the Current Status ofPetitions. This list is automatically updated and reflects all petitionsreceived to date by APHIS, including petitions pending, withdrawn, orapproved. Abbreviations: CMV—cucumber mosaic virus; CPB—colorado potatobeetle; PLRV—potato leafroll virus; PRSV—papaya ringspot virus;PVY—potato virus Y; WMV2—watermelon mosaic virus 2 ZYMV—zucchini yellowmosaic virus *** Extension of Petition Number: Under 7CFR 340.6(e) aperson may request that APHIS extend a determination of non-regulatedstatus to other organisms based on their similarity of the previouslyderegulated article. This column lists the previously granted petitionof that degregulated article. **** Preliminary EA: The EnvironmentalAssessment initially available for Public comment prior to finalization.

TABLE C Plant species Event Trait Patent reference Corn PV-ZMGT32(NK603) Glyphosate tolerance US 2007-056056 Corn MIR604 Insectresistance (Cry3a055) EP 1 737 290 Corn LY038 High lysine content U.S.Pat. No. 7,157,281 Corn 3272 Self processing corn (alpha- US 2006-230473amylase) Corn PV-ZMIR13 Insect resistance (Cry3Bb) US 2006-095986(MON863) Corn DAS-59122-7 Insect resistance US 2006-070139(Cry34Ab1/Cry35Ab1) Corn TC1507 Insect resistance (Cry1F) U.S. Pat. No.7,435,807 Corn MON810 Insect resistance (Cry1Ab) US 2004-180373 CornVIP1034 Insect resistance WO 03/052073 Corn B16 Glufosinate resistanceUS 2003-126634 Corn GA21 Glyphosate resistance U.S. Pat. No. 6,040,497Corn GG25 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GJ11Glyphosate resistance U.S. Pat. No. 6,040,497 Corn FI117 Glyphosateresistance U.S. Pat. No. 6,040,497 Corn GAT-ZM1 Glufosinate tolerance WO01/51654 Corn MON87460 Drought tolerance WO 2009/111263 Corn DP-098140-6Glyphosate tolerance/ALS WO 2008/112019 inhibitor tolerance Wheat Event1 Fusarium resistance CA 2561992 (trichothecene 3-O- acetyltransferase)Sugar beet T227-1 Glyphosate tolerance US 2004-117870 Sugar beet H7-1Glyphosate tolerance WO 2004-074492 Soybean MON89788 Glyphosatetolerance US 2006-282915 Soybean A2704-12 Glufosinate tolerance WO2006/108674 Soybean A5547-35 Glufosinate tolerance WO 2006/108675Soybean DP-305423-1 High oleic acid/ALS inhibitor WO 2008/054747tolerance Rice GAT-OS2 Glufosinate tolerance WO 01/83818 Rice GAT-OS3Glufosinate tolerance US 2008-289060 Rice PE-7 Insect resistance(Cry1Ac) WO 2008/114282 Oilseed rape MS-B2 Male sterility WO 01/31042Oilseed rape MS-BN1/RF-BN1 Male sterility/restoration WO 01/41558Oilseed rape RT73 Glyphosate resistance WO 02/36831 Cotton CE43-67BInsect resistance (Cry1Ab) WO 2006/128573 Cotton CE46-02A Insectresistance (Cry1Ab) WO 2006/128572 Cotton CE44-69D Insect resistance(Cry1Ab) WO 2006/128571 Cotton 1143-14A Insect resistance (Cry1Ab) WO2006/128569 Cotton 1143-51B Insect resistance (Cry1Ab) WO 2006/128570Cotton T342-142 Insect resistance (Cry1Ab) WO 2006/128568 Cottonevent3006-210-23 Insect resistance (Cry1Ac) WO 2005/103266 CottonPV-GHGT07 (1445) Glyphosate tolerance US 2004-148666 Cotton MON88913Glyphosate tolerance WO 2004/072235 Cotton EE-GH3 Glyphosate toleranceWO 2007/017186 Cotton T304-40 Insect-resistance (Cry1Ab) WO2008/122406Cotton Cot202 Insect resistance (VIP3) US 2007-067868 Cotton LLcotton25Glufosinate resistance WO 2007/017186 Cotton EE-GH5 Insect resistance(Cry1Ab) WO 2008/122406 Cotton event 281-24-236 Insect resistance(Cry1F) WO 2005/103266 Cotton Cot102 Insect resistance (Vip3A) US2006-130175 Cotton MON 15985 Insect resistance (Cry1A/Cry2Ab) US2004-250317 Bent Grass Asr-368 Glyphosate tolerance US 2006-162007Brinjal EE-1 Insect resistance (Cry1Ac) WO 2007/091277

Among the diseases of plants or crops that can be controlled by themethod according to the invention, mention can be made of:

Powdery mildew diseases such as:

-   -   Blumeria diseases, caused for example by Blumeria graminis;    -   Podosphaera diseases, caused for example by Podosphaera        leucotricha;    -   Sphaerotheca diseases, caused for example by Sphaerotheca        fuliginea;    -   Uncinula diseases, caused for example by Uncinula necator;

Rust diseases such as:

-   -   Gymnosporangium diseases, caused for example by Gymnosporangium        sabinae;    -   Hemileia diseases, caused for example by Hemileia vastatrix;    -   Phakopsora diseases, caused for example by Phakopsora pachyrhizi        or Phakopsora meibomiae;    -   Puccinia diseases, caused for example by Puccinia recondite,        Puccinia graminis or Puccinia striiformis;    -   Uromyces diseases, caused for example by Uromyces        appendiculatus;

Oomycete diseases such as:

-   -   Albugo diseases caused for example by Albugo candida;    -   Bremia diseases, caused for example by Bremia lactucae;    -   Peronospora diseases, caused for example by Peronospora pisi        or P. brassicae;    -   Phytophthora diseases, caused for example by Phytophthora        infestans;    -   Plasmopara diseases, caused for example by Plasmopara viticola;    -   Pseudoperonospora diseases, caused for example by        Pseudoperonospora humuli or Pseudoperonospora cubensis;    -   Pythium diseases, caused for example by Pythium ultimum;

Leafspot, leaf blotch and leaf blight diseases such as:

-   -   Alternaria diseases, caused for example by Alternaria solani;    -   Cercospora diseases, caused for example by Cercospora beticola;    -   Cladiosporum diseases, caused for example by Cladiosporium        cucumerinum;    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or        Cochliobolus miyabeanus;    -   Colletotrichum diseases, caused for example by Colletotrichum        lindemuthanium;    -   Cycloconium diseases, caused for example by Cycloconium        oleaginum;    -   Diaporthe diseases, caused for example by Diaporthe citri;    -   Elsinoe diseases, caused for example by Elsinoe fawcettii;    -   Gloeosporium diseases, caused for example by Gloeosporium        laeticolor;    -   Glomerella diseases, caused for example by Glomerella cingulata;    -   Guignardia diseases, caused for example by Guignardia bidwefli;    -   Leptosphaeria diseases, caused for example by Leptosphaeria        maculans; Leptosphaeria nodorum;    -   Magnaporthe diseases, caused for example by Magnaporthe grisea;    -   Mycosphaerella diseases, caused for example by Mycosphaerella        graminicola; Mycosphaerella arachidicola; Mycosphaerella        fijiensis;    -   Phaeosphaeria diseases, caused for example by Phaeosphaeria        nodorum;    -   Pyrenophora diseases, caused for example by Pyrenophora teres,        or Pyrenophora tritici repentis;    -   Ramularia diseases, caused for example by Ramularia collo-cygni,        or Ramularia areola;    -   Rhynchosporium diseases, caused for example by Rhynchosporium        secalis;    -   Septoria diseases, caused for example by Septoria apii or        Septoria lycopercisi;    -   Typhula diseases, caused for example by Typhula incamata;    -   Venturia diseases, caused for example by Venturia inaequalis;

Root, Sheath and stem diseases such as:

-   -   Corticium diseases, caused for example by Corticium graminearum;    -   Fusarium diseases, caused for example by Fusarium oxysporum;    -   Gaeumannomyces diseases, caused for example by Gaeumannomyces        graminis;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Sarocladium diseases caused for example by Sarocladium oryzae;    -   Sclerotium diseases caused for example by Sclerotium oryzae;    -   Tapesia diseases, caused for example by Tapesia acuformis;    -   Thielaviopsis diseases, caused for example by Thielaviopsis        basicola;

Ear and panicle diseases such as:

-   -   Alternaria diseases, caused for example by Alternaria spp.;    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Cladosporium diseases, caused for example by Cladosporium spp.;    -   Claviceps diseases, caused for example by Claviceps purpurea;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Monographella diseases, caused for example by Monographella        nivalis;

Smut and bunt diseases such as:

-   -   Sphacelotheca diseases, caused for example by Sphacelotheca        reiliana;    -   Tilletia diseases, caused for example by Tilletia caries;    -   Urocystis diseases, caused for example by Urocystis occulta;    -   Ustilago diseases, caused for example by Ustilago nuda;

Fruit rot and mould diseases such as:

-   -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Botrytis diseases, caused for example by Botrytis cinerea;    -   Penicillium diseases, caused for example by Penicillium        expansum;    -   Rhizopus diseases caused by example by Rhizopus stolonifer    -   Sclerotinia diseases, caused for example by Sclerotinia        sclerotiorum;    -   Verticilium diseases, caused for example by Verticilium        alboatrum;

Seed and soilborne decay, mould, wilt, rot and damping-off diseases:

-   -   Alternaria diseases, caused for example by Alternaria        brassicicola    -   Aphanomyces diseases, caused for example by Aphanomyces        euteiches    -   Ascochyta diseases, caused for example by Ascochyta lentis    -   Aspergillus diseases, caused for example by Aspergillus flavus    -   Cladosporium diseases, caused for example by Cladosporium        herbarum    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus    -   (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);    -   Colletotrichum diseases, caused for example by Colletotrichum        coccodes;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Macrophomina diseases, caused for example by Macrophomina        phaseolina    -   Monographella diseases, caused for example by Monographella        nivalis;    -   Penicillium diseases, caused for example by Penicillium expansum    -   Phoma diseases, caused for example by Phoma lingam    -   Phomopsis diseases, caused for example by Phomopsis sojae;    -   Phytophthora diseases, caused for example by Phytophthora        cactorum;    -   Pyrenophora diseases, caused for example by Pyrenophora graminea    -   Pyricularia diseases, caused for example by Pyricularia oryzae;    -   Pythium diseases, caused for example by Pythium ultimum;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Rhizopus diseases, caused for example by Rhizopus oryzae    -   Sclerotium diseases, caused for example by Sclerotium rolfsii;    -   Septoria diseases, caused for example by Septoria nodorum;    -   Typhula diseases, caused for example by Typhula incarnata;    -   Verticillium diseases, caused for example by Verticillium        dahliae;

Canker, broom and dieback diseases such as:

-   -   Nectria diseases, caused for example by Nectria galligena;

Blight diseases such as:

-   -   Monilinia diseases, caused for example by Monilinia laxa;

Leaf blister or leaf curl diseases such as:

-   -   Exobasidium diseases caused for example by Exobasidium vexans    -   Taphrina diseases, caused for example by Taphrina deformans;

Decline diseases of wooden plants such as:

-   -   Esca diseases, caused for example by Phaemoniella clamydospora;    -   Eutypa dyeback, caused for example by Eutypa lata;    -   Ganoderma diseases caused for example by Ganoderma boninense;    -   Rigidoporus diseases caused for example by Rigidoporus lignosus

Diseases of Flowers and Seeds such as

-   -   Botrytis diseases caused for example by Botrytis cinerea;

Diseases of Tubers such as

-   -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Helminthosporium diseases caused for example by Helminthosporium        solani;

Club root diseases such as

-   -   Plasmodiophora diseases, cause for example by Plamodiophora        brassicae.

Diseases caused by Bacterial Organisms such as

-   -   Xanthomonas species for example Xanthomonas campestris pv.        oryzae;    -   Pseudomonas species for example Pseudomonas syringae pv.        lachrymans;    -   Erwinia species for example Erwinia amylovora.

The composition according to the invention may also be used againstfungal diseases liable to grow on or inside timber. The term “timber”means all types of species of wood, and all types of working of thiswood intended for construction, for example solid wood, high-densitywood, laminated wood, and plywood. The method for treating timberaccording to the invention mainly consists in contacting one or morecompounds according to the invention or a composition according to theinvention; this includes for example direct application, spraying,dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatmentaccording to the invention is generally and advantageously from 10 to800 g/ha, preferably from 50 to 300 g/ha for applications in foliartreatment. The dose of active substance applied is generally andadvantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given asillustrative examples of the method according to the invention. A personskilled in the art will know how to adapt the application doses, notablyaccording to the nature of the plant or crop to be treated.

The compounds or mixtures according to the invention can also be usedfor the preparation of composition useful to curatively or preventivelytreat human or animal fungal diseases such as, for example, mycoses,dermatoses, trichophyton diseases and candidiases or diseases caused byAspergillus spp., for example Aspergillus fumigatus.

The various aspects of the invention will now be illustrated withreference to the following table of compound examples and the followingpreparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds offormula (I) according to the invention:

In table 1, unless otherwise specified, M+H (Apcl+) means the molecularion peak plus 1 a.m.u. (atomic mass unit) as observed in massspectroscopy via positive atmospheric pressure chemical ionisation.

In table 1, the logP values were determined in accordance with EECDirective 79/831 Annex V.A8 by HPLC (High Performance LiquidChromatography) on a reversed-phase column (C 18), using the methoddescribed below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid andacetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3to 16 carbon atoms) with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones). lambda-max-values were determined usingUV-spectra from 200 nm to 400 nm and the peak values of thechromatographic signals.

TABLE 1     Example     X¹     X²     T     n

    Z³     Q¹     B     logP   Mass (M + H)  1 Cl F O 0 — H —2-methylphenyl 2.90 354  2 F F O 0 — H — 2-methylphenyl 2.75 338  3 F FO 0 — H — 2-methoxyphenyl 2.59 354  4 F F O 0 — H — 4-methoxyphenyl 2.42354  5 Cl F O 0 — H — 2-chlorophenyl 3.04 374  6 F F O 0 — H —2-chlorophenyl 2.90 358  7 Cl F O 0 — H — 4-chlorophenyl 3.04 374  8 F FO 0 — H — 4-chlorophenyl 2.90 358  9 Cl F O 0 — H — 3,5-difluorophenyl2.82 376 10 F F O 0 — H — 3,5-difluorophenyl 2.70 360 11 F F O 0 — H —1,3-benzodioxol-5-yl 2.35 368 12 Cl F O 0 — H — 4-tert-butylphenyl 3.90396 13 F F O 0 — H — 4-tert-butylphenyl 3.74 380 14 Cl F O 0 — H —2-(trifluoromethyl) 3.19 408 phenyl 15 F F O 0 — H — 2-(trifluoromethyl)3.09 392 phenyl 16 Cl F O 0 — H — 3-(trifluoromethyl) 3.21 408 phenyl 17F F O 0 — H — 3-(trifluoromethyl) 3.06 392 phenyl 18 F F S 0 — H —3-(trifluoromethyl) 3.59 408 phenyl 19 Cl F S 0 — H —3-(trifluoromethyl) 3.79 424 phenyl 20 Cl F O 0 — H —4-(trifluoromethyl) 3.25 408 phenyl 21 F F O 0 — H — 4-(trifluoromethyl)3.13 392 phenyl 22 F F O 0 — H — 2,4-dichlorophenyl 3.44 392 23 Cl F O 0— H — 2,4-dichlorophenyl 3.57 408 24 F F S 0 — H — 2,4-dichlorophenyl4.09 408 25 Cl F O 0 — H — 3,4-dichlorophenyl 3.37 408 26 F F O 0 — H —3,4-dichlorophenyl 3.23 392 27 Cl F O 0 — H — 3,5-dichlorophenyl 3.50408 28 F F O 0 — H — 3,5-dichlorophenyl 3.35 392 29 F F O 0 — H —biphenyl-4-yl 3.50 400 30 Cl F O 0 — H — biphenyl-4-yl 3.65 416 31 Cl FO 0 — H — 2-bromophenyl 3.09 418 32 F F O 0 — H — 2-bromophenyl 2.98 40233 Cl F O 0 — H — 3-bromophenyl 3.06 418 34 F F O 0 — H — 3-bromophenyl2.92 402 35 Cl F O 0 — H — 3-(trifluoromethoxy) 3.33 424 phenyl 36 F F O0 — H — 3-(trifluoromethoxy) 3.21 408 phenyl 37 Cl F O 0 — H —3-(trifluoromethoxy) 3.31 424 phenyl 38 F F O 0 — H —3-(trifluoromethoxy) 3.17 408 phenyl 39 F F O 0 — H — 3,5-bis(trifluoro-3.63 460 methylphenyl) 40 Cl F O 0 — H — 3,5-bis(trifluoro- 3.79 476methyl)phenyl 41 F F O 0 — H — 1-naphthyl 3.08 374 42 F F O 0 — H —2-furyl 2.13 314 43 F F O 0 — H — pyridin-2-yl 0.92 325 44 F F O 0 — H —pyridin-3-yl 0.48 325 45 F F O 0 — H — 2-thienyl 2.39 330 46 F F O 0 — H— quinolin-3-yl 1.50 375 47 F F O 0 — H — quinolin-6-yl 1.14 375 48 F FO 0 — H — 1-benzothiophen-2-yl 3.11 380 49 Cl F O 0 — H —1-benzothiophen-2-yl 3.25 396 50 Cl F O 0 — H — 1,3-benzothiazol-2-yl2.61 397 51 F F O 0 — H — 1,3-benzothiazol-2-yl 2.49 381 52 F F O 1—CH₂— H — phenyl 2.84 338 53 F F O 1 —CH(Et)— H — phenyl 3.48 366 54 F FO 1 —CH₂— H — 2-methylphenyl 3.13 352 55 F F O 1 —CH₂— H —3-methylphenyl 3.21 352 56 F F O 1 —CH₂— H — 4-methylphenyl 3.23 352 57F F O 1 —CH₂— H — 2-fluorophenyl 2.86 356 58 F F O 1 —CH₂— H —3-fluorophenyl 2.90 356 59 F F O 1 —CH₂— H — 4-fluorophenyl 2.90 356 60F F O 1 —CH₂— H — 2-chlorophenyl 3.06 372 61 F F S 1 —CH₂— H —2-chlorophenyl 3.83 388 62 F F O 1 —CH(Me)— H — 2-chlorophenyl 3.29 38663 Cl F O 1 —CH(Me)— H — 2-chlorophenyl 3.46 402 64 F F O 1 —CH₂— H —3-chlorophenyl 3.25 372 65 F F O 1 —CH₂— H — 4-chlorophenyl 3.29 372 66F F O 1 —CH₂— H — 2,4,5-trimethylphenyl 3.81 380 67 F F O 1 —CH₂— H —2-chloro-6-fluoro 3.15 390 phenyl 68 F F O 1 —CH₂— H —4-tert-butylphenyl 4.24 394 69 F F O 1 —CH₂— H — 2,3-dichlorophenyl 3.64406 70 F F S 1 —CH₂— H — 2,3-dichlorophenyl 4.46 422 71 F F O 1 —CH(Me)—H — 2,4-dichlorophenyl 3.87 420 72 Cl F O 1 —CH(Me)— H —2,4-dichlorophenyl 4.06 436 73 F F O 1 —CH(Me)— H — 2,5-dichlorophenyl3.76 420 74 Cl F O 1 —CH(Me)— H — 2,5-dichlorophenyl 3.96 436 75 Cl F O1 —CH₂— H — 2,6-dichlorophenyl 3.50 422 76 F F O 1 —CH₂— H —2,6-dichlorophenyl 3.31 406 77 F F S 1 —CH₂— H — 2,6-dichlorophenyl 4.06422 78 F F O 1 —CH(Me)— H — 2,6-dichlorophenyl 3.52 420 79 Cl F O 1—CH(Me)— H — 2,6-dichlorophenyl 3.81 436 80 F F O 1 —CH₂— H —4-bromophenyl 3.39 416 81 Cl F O 1 (S)-CH₂—⁽¹⁾ H O 2,4,6-trichlorophenyl4.36 472 82 F F O 1 (S)-CH₂—⁽¹⁾ H O 2,4,6-trichlorophenyl 4.24 456 83 FF O 1 —CH₂— H — 1-naphthyl 3.52 388 84 F F O 2 —CH₂CH₂— H — phenyl 3.02352 85 F F O 1 (S)-CH₂—⁽¹⁾ H O 4-chlorophenyl 3.29 388 86 Cl F O 1(S)-CH₂—⁽¹⁾ H O 4-chlorophenyl 3.44 404 87 F F O 1 —CH₂— H SO₂ phenyl2.13 402 88 Cl F O 1 —CH₂— H SO₂ phenyl 2.20 418 note 1: (S) enantiomer

The following examples illustrate in a non-limiting manner thepreparation and efficacy of the compounds of formula (I) according tothe invention.

PREPARATION EXAMPLE 1 Preparation of[3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl][2-(3-methyl-benzyl)pyrrolidin-1-yl]methanone(compound 55) Step 1: preparation of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(IIIa-1)

In a 500 ml flask, 6.0 g (31 mmol) of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde areadded to 30 ml of toluene. A solution of 2.4 g (62 mmol) of sodiumhydroxide in 6 ml of water is added to the reaction mixture, followed by103 ml of a 30% solution of hydrogen peroxide in water, whilst keepingthe temperature below 37° C. After the end of the addition, the reactionmixture is stirred at 50° C. for 7 hours. Once the reaction mixture isback to room temperature, the two phases are separated and the organicphase is extracted with 100 ml of water. The combined aqueous phases areacidified to pH 2 with aqueous hydrochloric acid. The resulting whiteprecipitate is filtered, washed twice with 20 ml of water, and dried toyield 3.2 g of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid. ¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.78 (s, 3H); 7.12 (t, 1H,JHF=53.60 Hz) 13.19 (s, 1H); IR (KBr): 1688 cm⁻¹ (C═O); 2200-3200 cm⁻¹broad (hydrogen bond).

Step 2: preparation of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride(IIIb-1)

3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylicacid and 44.3 ml of thionyl chloride are refluxed for 5 hours. Aftercooling down, the reaction mixture is evaporated under vacuum to yield3.5 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil. ¹H NMR (400 MHz, CHCl3-d₆) δ ppm: 3.97 (s,3H); 7.00 (t, J=52.01 Hz, 1H); IR (TQ): 1759 and 1725 cm⁻¹ (C═O).

Step 3: preparation of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride(IIIc-1)

To a dried solution of 4.0 g (70 mmol) of potassium fluoride in 21 ml oftetrahydrothiophene-1,1-dioxide is added a solution of 5.0 g (22 mmol)of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloridein 15 ml of toluene at 100° C. The resulting reaction mixture is stirredat 190-200° C. for 22 hours. Distillation under vacuum yields 8 g of asolution (25% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydrothiophene-1,1-dioxide. ¹H NMR (250 MHz, CHCl₃-d₆) δ ppm: 3.87(s, 3H); 6.79 (t, J=53.75 Hz, 1H); ¹⁹F NMR (250 MHz, CHCl₃-d₆) δ ppm:45.37 (s, COF); −117.5 (d, J=28.2 Hz); −131.6 (m).

Step 4: preparation of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid(IIId-1)

To 400 ml of a 1N sodium hydroxide aqueous solution, is added dropwise67.5 g of a solution (10% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydrothiophene-1,1-dioxide. The temperature is kept below 20° C.during the addition. After 2 hours of stirring at room temperature, thereaction mixture is carefully acidified to pH 2 with concentratedaqueous hydrochloric acid. The resulting white precipitate is filtered,washed with water, and dried to yield 6 g of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid. ¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.90 (s, 3H); 7.22 (t, 1H,J_(HF)=53.55 Hz); 13.33 (s, 1H).

Step 5: preparation of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride(IIIe-1)

9.1 g of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylicacid and 75.5 ml of thionyl chloride are refluxed for 1.5 hours. Aftercooling down, the reaction mixture is evaporated under vacuum to yield10 g of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil. GC-MS; observed M/z:Molecular ion:(M^(+.))=212; fragments: (M^(+.)−Cl)=177 and (M^(+.)−F)=193.

Step 6: preparation of[3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl][2-(3-methylbenzyl)pyrrolidin-1-yl]methanone

At ambient temperature, a solution of 267 mg (1.25 mmol) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride in1 ml of tetrahydrofurane is added dropwise to a solution of 200 mg (1.14mmol) of 2-(3-methylbenzyl)pyrrolidine and 127 mg (1.25 mmol) oftriethylamine in 5 ml of tetra-hydrofurane. The reaction mixture isstirred for 1 hour at 70° C. The solvent is removed under vacuum and 100ml of water are then added to the residue. The watery layer is extractedtwice with ethyl acetate (2×150 ml) and the combined organic layers aresuccessively washed by a 1 N solution of HCl, a saturated solution ofpotassium carbonate and filtered over a Chemelut™ cardridge to yieldafter concentration 350 mg of a beige oil. Column chromatography onsilica gel (gradient heptane/ethyl acetate) yields 300 mg (71% yield) of[3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl][2-(3-methylbenzyl)pyrrolidin-1-yl]-methanoneas a colourless oil (M+H=352).

GENERAL PREPARATION EXAMPLE 2 Thionation of Amide of Formula (I) onChemspeed™ Apparatus

In a 13 ml Chemspeed™ vial is weighted 0.27 mmol of phosphorouspentasulfide (P₂S₅). 3 ml of a 0.18 molar solution of the amide (I)(0.54 mmol) in dioxane is added and the mixture is heated at reflux fortwo hours. The temperature is then cooled to 80° C. and 2.5 ml of waterare added. The mixture is heated at 80° C. for one more hour. 2 ml ofwater are then added and the reaction mixture is extracted twice by 4 mlof dichloromethane. The organic phase is deposited on a basic aluminacartridge (2 g) and eluted twice by 8 ml of dichloromethane. Thesolvents are removed and the crude thioamide derivative is analyzed byLCMS and NMR. Insufficiently pure compounds are further purified bypreparative LCMS.

Example A In Vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Sphaerotheca fuliginea. Then the plants are placedin a greenhouse at approximately 23° C. and a relative atmospherichumidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table A:

TABLE A Example Efficacy 2 95 6 90 10 85 13 93 16 86 17 95 18 100 21 8122 91 24 95 26 95 27 70 28 100 32 95 34 95 36 90 38 95 39 100 41 75 4893 53 93 54 95 55 95 56 81 57 94 58 96 59 93 60 95 61 95 64 93 65 95 6688 67 95 69 88 76 95 77 95 80 89 81 100 82 100

Example B In Vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Alternaria solani. The plants remain for one day inan incubation cabinet at approximately 22° C. and a relative atmospherichumidity of 100%. Then the plants are placed in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table B:

TABLE B Example Efficacy 1 80 2 90 3 80 4 80 5 80 6 100 7 95 8 100 10 9512 90 13 100 14 95 15 95 16 100 17 100 18 90 20 70 21 90 22 100 23 95 2490 25 95 26 95 27 95 28 95 29 95 31 90 32 95 33 95 34 95 35 95 36 100 3790 38 100 39 95 40 95 45 90 52 100 53 94 54 94 56 94 57 94 58 89 60 10061 100 65 94 66 100 67 100 68 94 69 100 70 95 75 90 76 95 77 100 80 10083 100 84 90

Under the same conditions, excellent (at least 90%) protection isobserved at a dose of 500 ppm and 100 ppm of active ingredient withcompound 76, whereas excellent (at least 90%) to poor (less than 30%)protection is observed with the compound of example 1.110 disclosed inpatent application WO-2009/153191 as in table B2.

TABLE B2 Example dose (ppm) Efficacy 76 from this invention 500 95 10090 1.110 from WO-2009/153191 500 95 100 30

Example 1.110 disclosed in international patent WO-2009/153191corresponds to[2-(2,6-dichlorobenzyl)pyrrolidin-1-yl][3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]methanone.

These results show that the compounds according to the invention have abetter biological activity than the structurally closest compoundsdisclosed in WO-2009/153191.

Example C In Vivo Preventive Test on Pyrenophora teres (Barley)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Pyrenophora teres. The plants remain for 48 hours inan incubation cabinet at 22° C. and a relative atmospheric humidity of100%. Then the plants are placed in a greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table C:

TABLE C Example Efficacy 1 80 2 100 5 80 6 100 7 70 8 100 9 90 10 100 1170 12 95 13 100 14 90 15 100 16 100 17 100 18 100 19 100 20 70 21 95 2295 23 100 24 100 25 95 26 100 27 95 28 100 29 100 30 100 31 95 32 100 33100 34 100 35 95 36 100 37 100 38 100 39 100 40 95 41 90 45 95 48 100 4995 51 95 52 100 53 100 54 95 55 100 56 100 57 100 58 100 59 100 60 10061 100 64 100 65 100 66 100 67 100 68 100 69 100 70 100 75 100 76 100 77100 80 100 83 100 84 100

Example D In Vivo Preventive Test on Venturia inaequalis (Apple Scab)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the causal agent of apple scab (Venturiainaequalis) and then remain for 1 day in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, excellent (at least 98%) to total protection isobserved at a dose of 100 ppm of active ingredient with the followingcompounds from table D:

TABLE D Example Efficacy 52 100 53 100 54 100 55 100 56 98 57 100 58 9960 100 64 100 65 100 66 100 67 100

Example E In Vivo Preventive Test on Septoria tritici (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Septoria tritici. The plants remain for 48 hours inan incubation cabinet at approximately 20° C. and a relative atmospherichumidity of approximately 100% and afterwards for 60 hours atapproximately 15° C. in a translucent incubation cabinet at a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 15° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 21 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, excellent (at least 90%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table E:

TABLE E Example Efficacy 52 100 53 100 54 100 55 100 56 100 57 100 58100 59 90 64 100 65 100 66 90 67 100 76 83 82 86

Example F In Vivo Preventive Test on Blumeria graminis (Barley)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are dusted withspores of Blumeria graminis f.sp. hordei.

The plants are placed in the greenhouse at a temperature ofapproximately 18° C. and a relative atmospheric humidity ofapproximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, total protection is observed at a dose of 500ppm of active ingredient with the following compounds from table F:

TABLE F Example Efficacy 52 100 53 100 54 100 55 100 56 100 57 100 58100 59 100 60 100 64 100 65 100 67 100 76 100 82 100

Example G In Vivo Preventive Test on Fusarium nivale (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are slightly injuredby using a sandblast and afterwards they are sprayed with a conidiasuspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 10° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, total protection is observed at a dose of 500ppm of active ingredient with the following compounds from table G:

TABLE G Example Efficacy 52 100 53 100 54 100 55 100 56 100 57 100 58100 59 100 60 100 64 100 65 100 66 100 67 100 76 100 82 100

Example H In Vivo Preventive Test on Leptosphaeria nodorum (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Leptosphaeria nodorum. The plants remain for 48hours in an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 22° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, excellent (at least 90%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table H:

TABLE H Example Efficacy 52 100 53 100 54 100 55 100 56 93 57 100 58 10059 93 60 100 64 93 65 100 67 100 76 100 82 94

Under the same conditions, high (at least 85%) protection to poor (lessthan 50%) protection is observed at a dose of 500 ppm and 100 ppm ofactive ingredient with compound 76, whereas poor (less than 50%)protection to no protection is observed with the compound of example1.110 disclosed in patent application WO-2009/153191 as in table H2.

TABLE H2 Example dose (ppm) Efficacy 76 from this invention 500 89 10033 1.110 from WO-2009/153191 500 44 100 0

Example 1.110 disclosed in international patent WO-2009/153191corresponds to[2-(2,6-dichlorobenzyl)pyrrolidin-1-yl][3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]methanone.

These results show that the compounds according to the invention have abetter biological activity than the structurally closest compoundsdisclosed in WO-2009/153191.

Under the same conditions, high (at least 85%) protection is observed ata dose of 500 ppm and 250 ppm of active ingredient with compound 82,whereas good (at least 70%) protection to poor (less than 50%)protection is observed with the compound of example 1.006 disclosed inpatent application WO-2009/153191 as in table H3.

TABLE H3 Example dose (ppm) Efficacy 82 from this invention 500 94 25088 1.006 from WO-2009/153191 500 71 250 43

Example 1.006 disclosed in international patent WO-2009/153191corresponds to[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]{(S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone.

These results show that the compounds according to the invention have abetter biological activity than the structurally closest compoundsdisclosed in WO-2009/153191.

Example I In Vivo Preventive Test on Puccinia triticina (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Puccinia triticina. The plants remain for 48 hoursin an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, high (at least 85%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table I:

TABLE I Example Efficacy 52 89 53 88 54 100 55 100 56 89 57 100 58 10059 88 60 100 64 100 66 100 67 94 82 100

Example J In Vivo Protective Test on Pyricularia oryzae (Rice)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after spraying, the plants are inoculated with an aqueous sporesuspension of the causal agent of rice blast (Pyricularia oryzae). Theplants are then placed in an incubator at approximately 25° C. and arelative atmospheric humidity of approximately 100% for 1 day.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, while an efficacy of 100%means that no disease is observed.

Under these conditions, excellent (at least 90%) protection is observedat a dose of 250 ppm of active ingredient with the following compoundsfrom table J:

TABLE J Example Efficacy 17 92 66 97 82 98

Example K In Vivo Protective Test on Rhizoctonia solani (Rice)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after spraying, the plants are inoculated with a hypha of the causalagent of rice sheath blight (Rhizoctonia solani). The plants are thenplaced in an incubator at approximately 25° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 4 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, while an efficacy of 100%means that no disease is observed.

Under these conditions, high (at least 80%) or total protection isobserved at a dose of 250 ppm of active ingredient with the followingcompounds from table K:

TABLE K Example Efficacy 66 80 82 100

Example L In Vivo Protective Test on Cochliobolus miyabeanus (Rice)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after spraying, the plants are inoculated with an aqueous sporesuspension of the causal agent of rice brown spot (Cochliobolusmiyabeanus). The plants are then placed in an incubator at approximately25° C. and a relative atmospheric humidity of approximately 100% for 1day.

The test is evaluated 4 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, while an efficacy of 100%means that no disease is observed.

Under these conditions, excellent (at least 90%) protection is observedat a dose of 250 ppm of active ingredient with the following compoundsof table L:

TABLE L Example Efficacy 17 98 53 95 66 98 82 93

Example M In Vivo Protective Test on Phakopsora pachyrhizi (Soybeans)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after spraying, the plants are inoculated with an aqueous sporesuspension of the causal agent of soybean rust (Phakopsora pachyrhizi).The plants are then placed in a greenhouse at approximately 20° C. and arelative atmospheric humidity of approximately 80%.

The test is evaluated 11 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of100% means that no disease is observed.

Under these conditions, high (85%) protection is observed at a dose of250 ppm of active ingredient with the following compound: 53.

1. A compound of formula (I):

wherein T represents O or S; X¹ and X² which can be the same ordifferent, represent a chlorine or a fluorine atom; n represents 0, 1 or2; Q¹ represents a bond; O; S; SO; or SO₂; B represents a phenyl ringthat can be substituted by up to 5 groups X which can be the same ordifferent; a naphthyl ring that can be substituted by up to 7 groups Xwhich can be the same or different; or a saturated, partially saturatedor unsaturated, monocyclic or fused bicyclic 4-, 5-, 6-, 7-, 8-, 9-,10-membered ring comprising from 1 up to 4 heteroaroms selected in thelist consisting of N, O, S, that can be substituted by up to 6 groups Xwhich can be the same or different; X represents a halogen atom; nitro;cyano; isonitrile; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;formyl; formyloxy; formylamino; substituted or non-substituted(hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted(C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted(C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or non-substituted(C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted or non-substituted(benzyloxyimino)-C₁-C₈-alkyl; carboxy; carbamoyl; N-hydroxycarbamoyl;carbamate; substituted or non-substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted ornon-substituted C₂-C₈-alkenyl; C₂-C₈-halogenoalkenyl having 1 to 5halogen atoms; substituted or non-substituted C₂-C₈-alkynyl;C₂-C₈-halogenoalkynyl having 1 to 5 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having1 to 5 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5 halogenatoms; substituted or non-substituted C₁-C₈-alkylamino; substituted ornon-substituted di-C₁-C₈-alkylamino; substituted or non-substitutedC₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1 to 5 halogen atoms;substituted or non-substituted C₃-C₈-alkynyloxy;C₂-C₈-halogenoalkynyloxy having 1 to 5 halogen atoms; substituted ornon-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 5halogen atoms; substituted or non-substituted(C₃-C₇-cycloalkyl)-C₁-C₈-alkyl; substituted or non-substituted(C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl; substituted or non-substituted(C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl; substituted or non-substitutedtri(C₁-C₈)alkylsilyl; substituted or non-substitutedtri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogenatoms; substituted or non-substituted C₁-C₈-alkylcarbonyloxy;C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkyl-carbonylamino having 1 to 5 halogen atoms;substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms; substituted ornon-substituted C₁-C₈-alkyloxycarbonyloxy;C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; substituted or non-substitutedC₁-C₈-alkylaminocarbonyloxy; substituted or non-substituteddi-C₁-C₈-alkylaminocarbonyloxy; substituted or non-substitutedN—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or non-substitutedC₁-C₈-alkoxycarbamoyl; substituted or non-substitutedN—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that can be substituted byup to 6 groups Q which can be the same or different; C₁-C₈-arylalkylthat can be substituted by up to 6 groups Q which can be the same ordifferent; C₂-C₈-arylalkenyl that can be substituted by up to 6 groups Qwhich can be the same or different; C₂-C₈-arylalkynyl that can besubstituted by up to 6 groups Q which can be the same or different;aryloxy that can be substituted by up to 6 groups Q which can be thesame or different; arylsulfanyl that can be substituted by up to 6groups Q which can be the same or different; arylamino that can besubstituted by up to 6 groups Q which can be the same or different;C₁-C₈-arylalkyloxy that can be substituted by up to 6 groups Q which canbe the same or different; C₁-C₈-arylalkylsulfanyl that can besubstituted by up to 6 groups Q which can be the same or different; orC₁-C₈-arylalkylamino that can be substituted by up to 6 groups Q whichcan be the same or different; two substituent X together with theconsecutive carbon atoms to which they are linked can form a 5- or6-membered, saturated carbocycle or saturated heterocycle, which can besubstituted by up to four groups Q which can be the same or different;Z¹ and Z² independently represent a hydrogen atom; a halogen atom;cyano; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkylhaving 1 to 5 halogen atoms; substituted or non-substitutedC₁-C₈-alkoxy; substituted or non-substituted C₁-C₈-alkylsulfanyl; orsubstituted or non-substituted C₁-C₈-alkoxycarbonyl; or two substituentsZ¹ and Z², together with the carbon atom to which they are linked canform a 3-, 4-, 5- or 6-membered saturated carbocycle that can besubstituted by up to four C₁-C₈-alkyl groups; Z³ represent a hydrogenatom; or substituted or non-substituted C₁-C₈-alkyl; Q independentlyrepresents a halogen atom; cyano; nitro; substituted or non-substitutedC₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms that can bethe same or different; substituted or non-substituted C₁-C₈-alkoxy;C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms that can be the same ordifferent; substituted or non-substituted C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogen atoms that can be thesame or different; substituted or non-substituted tri(C₁-C₈)alkylsilyl;substituted or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; as well asits salts, N-oxides, metal complexes, metalloid complexes and opticallyactive isomers.
 2. A compound according to claim 1 wherein X¹ representsa fluorine atom.
 3. A compound according to claim 1 wherein X²represents a fluorine atom.
 4. A compound according to claim 1 wherein Trepresents O.
 5. A compound according to claim 1 wherein n represents 0or
 1. 6. A compound according to claim 1 wherein Q¹ represents a bond oran oxygen atom.
 7. A compound according to claim 6 wherein Q¹ representsa bond.
 8. A compound according to claim 1 wherein B represents asubstituted or non-substituted phenyl ring; a substituted ornon-substituted naphthyl ring; a substituted or non-substituted pyridylring; a substituted or non-substituted thienyl ring; or a substituted ornon-substituted benzothienyl ring.
 9. A compound according to claim 8wherein B represents a substituted or non-substituted phenyl ring.
 10. Acompound according to claim 8 wherein B represents a substituted ornon-substituted naphthyl ring.
 11. A compound according to claim 1wherein X independently represents a halogen atom; substituted ornon-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; substituted ornon-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different; or wherein twoconsecutive substituents X together with the phenyl ring form asubstituted or non substituted 1,3-benzodioxolyl or 1,4-benzodioxanylring.
 12. A compound according to claim 1 wherein Z¹ and Z²independently represents a hydrogen atom, a halogen, substituted ornon-substituted C₁-C₈-alkyl or substituted or non-substitutedC₁-C₈-alkoxy.
 13. A compound according to claim 1 wherein Z³ representsa hydrogen atom.
 14. A fungicide composition comprising, as an activeingredient, an effective amount of a compound of formula (I) accordingto claim 1 and an agriculturally acceptable support, carrier or filler.15. A method for controlling phytopathogenic fungi of crops,characterized in that an agronomically effective and substantiallynon-phytotoxic quantity of a compound according to claim 1 is applied tothe soil where plants grow or are capable of growing, to the leavesand/or the fruit of plants or to the seeds of plants.
 16. A method forcontrolling phytopathogenic fungi of crops, characterized in that anagronomically effective and substantially non-phytotoxic quantity of afungicide composition according to claim 14 is applied to the soil whereplants grow or are capable of growing, to the leaves and/or the fruit ofplants or to the seeds of plants.